Sample records for amorphous hydrogenated carbon

Amorphoushydrogenatedcarbon films (-C:H) on -type (100) silicon wafers were prepared with a middle frequency pulsed unbalanced magnetron sputtering technique (MFPUMST) at different ratios of methane–argon gases. The band characteristics, mechanical properties as well as refractive index were measured by ...

Carbon can be formed either as fully crystalline structures, such as diamond, graphite, and fullerene (C60). or as mostly amorphous structures, like amorphoushydrogenatedcarbon (a-C:H). A study was made of a-C:H films which had been deposited by plasma enhanced chemical vapor deposition (PECVD) using CH4, H2 and Ar (or N2 for doping) gas mixtures. Each film exhibits unique physical, optical and electronic properties dependent upon the specific deposition parameters. The study is intended to extend our understanding of the properties of a-C:H films. Samples prepared by James Johnson, similar to those used in his previous studies (using mainly 4 separate sets of deposition parameters), were evaluated along with other samples which were unique to this study. Film preparation parameters were varied to allow an examination of the effects induced through the variation of deposition power level, partial substitution of nitrogen for methane in the deposition process gasses and post-deposition thermal annealing. The film optical properties were evaluated using combination of non-destructive test methods, including Raman scattering, photoluminescence (PL), optical absorption and photoluminescence excitation (PLE) spectroscopies. Different PL responses at low temperature (6 K) were recorded for doped and/or annealed samples deriving from the main set of samples. Two new features at 564 and 637 nm of nitrogen doped films replaced the 597 and 703 nm of undoped films. For the first time, three Raman phonon peaks were observed in a nitrogen doped and annealed film. Additional FTIR data indicated that the third Raman phonon peak was associated with CH2 and CH3 bonding structures. The Raman scattering data contributed to an improved understanding of the two-phase (sp2, sp3) model developed by Robertson. Optical absorption measurements could only be obtained for the films deposited on fused quartz. All other measurements were made on films deposited on silicon, which is opaque in

In a previous study, it was demonstrated that an amorphouscarbon layer, deposited on a native oxide covered uranium surface, significantly enhances the interaction of hydrogen with the uranium metal. Fig. 1[2], demonstrates the preferential hydrogen attack (forming uranium hydride) on the carbon covered area of the naturally oxidized uranium metal

One of the main safety problems in the ITER tokamak project is the tritium adsorption in the reactor walls and in particular the deposits which appear after the plasma discharge. These deposits are amorphoushydrogenatedcarbon films, type polymer (soft a-C:H). The heating of these deposits with a pulse laser is a proposed solution for the tritium desorption. Meanwhile, Gibson and al show that in experimental conditions, products are deposed on the walls before entering the mass spectrometer. The authors present thermo-desorption spectra of different amorphouscarbon films. (A.L.B.)

Amorphous fluorinated carbon films were grown from CF 4 and C 2H 2 mixtures, using a Plasma Assisted Chemical Vapour Deposition (PACVD) apparatus. Two sets of films were deposited, changing in a systematic way the CF 4 flux and the bias voltage ( Vb). Film composition and structure were analysed by secondary ion mass spectroscopy (SIMS), infrared (IR) and Raman spectroscopies. Film hardness was obtained by micro-indentation measurements. On increasing fluorine content in films, hardness decreases and a fluorescence background in Raman spectra appears at high fluorine content, showing a diamond- to polymer-like structural transition. Infrared spectra indicate the presence of CF x, CCHF and CCF 2 groups in the films. Our data are compared with previous results in the literature and the mechanisms involved in film formation are discussed, especially regarding fluorine substitution for hydrogen.

The infrared analysis of thin films on a thick substrate is discussed using the example of plasma-deposited, amorphous, hydrogenatedcarbon layers (a-C:H) on silicon substrates. The framework for the optical analysis of thin films is presented. The main characteristic of thin film optics is the occurrence of interference effects due to the coherent superposition of light multiply reflected at the various internal and external interfaces of the optical system. These interference effects lead to a sinusoidal variation of the transmitted and reflected intensity. As a consequence, the Lambert-Beer law is not applicable for the determination of the absorption coefficient of thin films. Furthermore, observable changes of the transmission and reflection spectra occur in the vicinity of strong absorption bands due to the Kramers-Kronig relation. For a sound data evaluation these effects have to be included in the analysis. To be able to extract the full information contained in a measured optical thin film spectrum, ...

In this paper we report on the transport properties of hydrogenatedamorphouscarbon (a-C:H) which is an attractive material for strain gauges and can also be used in flow meters, accelerometers and vibrational sensors. The a-C:H films were deposited at -350 V bias voltage on silicon (Si) substrates using plasma assisted chemical vapor deposition (PACVD). Current-voltage characteristics of a-C:H/n-Si heterojunctions show ohmic behavior within operating voltages of ±1 V. In the higher voltage range the Frenkel-Poole mechanism is dominant. Conduction is thermally activated at temperatures ranging from 23 °C to 150 °C. The activation energy amounts to 0.48 eV. A-C:H resistors are successfully integrated as strain gauges in Si bulk micromachined force sensors. Piezoresistive gauge factors are measured for the a-C:H strain gauge resistors in the temperature range 23-60 °C. The measured piezoresistive gauge factors are in between 40 and 90 for a-C:H with resistivities in the range 100-700 MΩ cm.

Author.Hydrogenatedamorphouscarbon (a-C:H) films presently attract considerable interest because of their potential applications in the domain of multifunctional coatings: transparent in the infrared, very hard, chemically inert, etc...This material is rather complex since it contains C atoms in both sp 3 (diamond) and sp 2 (graphite) electronic configurations, as well as a large concentration of H atoms. Its properties are strongly dependent on the deposition conditions which determine the film microstructure, i.e. the relative proportions of sp 3 and sp 2 C sites, their connection in the network and the hydrogen bonding modes. It has been suggested that the sp 2 C sites tend to cluster into unsaturated chains ans rings, which are then embedded in the sp 3 C sites m atrix . Hydrogen incorporation plays a crucial role in this intrinsic microheterogeneity, which determines the electronic properties, and especially the gap value, of a-C:H. We here present and discuss the results of Fourrier transform infrared absorption spectroscopy measurements performed on a-C:H films prepared under different conditions and submitted to controlled annealing cycles, which exhibit quite different optical gap values (from 1 to 2.5 eV). We carefully analyze the absorption bands detected in the 400-7500 cm -1 spectral range in terms of the vibration modes of C-H and C-C bonds in different local environments and we interpret the results in relation with the film microstructure and optical properties. Special attention is also paid to the absorption background and to the variations of the whole absorption spectra with measurement temperature

Thin ion-plated amorphoushydrogenatedcarbon films were investigated by electron energy loss spectroscopy. From an analysis of the dielectric function, information on the film structure could be obtained. The results will be compared with those of electron diffraction studies. Differences between insulating and conducting substrates could be verified in the film structure and are related to surface charging effects. From an analysis of the oscillator strength sum rule the content of C sp{sup 2} atoms was estimated. (orig.).

Full Text Available The evolution of hydrogenatedamorphouscarbon films with fullerene-like microstructure was investigated with a different proportion of hydrogen supply in deposition. The results showed at hydrogen flow rate of 50 sccm, the deposited films showed a lower compressive stress (lower 48.6%, higher elastic recovery (higher 19.6%, near elastic recovery rate 90%, and higher hardness (higher 7.4% compared with the films deposited without hydrogen introduction. Structural analysis showed that the films with relatively high sp2 content and low bonded hydrogen content possessed high hardness, elastic recovery rate, and low compressive stress. It was attributed to the curved graphite microstructure, which can form three-dimensional covalently bonded network.

The structural aspects of amorphous silicon and the role of hydrogen in this structure are reviewed with emphasis on ion implantation studies. In amorphous silicon produced by Si ion implantation of crystalline silicon, the material reconstructs into a metastable amorphous structure which has optical and electrical properties qualitatively similar to the corresponding properties in high-purity evaporated amorphous silicon. Hydrogen studies further indicate that these structures will accomodate less than or equal to 5 at.% hydrogen and this hydrogen is bonded predominantly in a monohydride (SiH 1 ) site. Larger hydrogen concentrations than this can be achieved under certain conditions, but the excess hydrogen may be attributed to defects and voids in the material. Similarly, glow discharge or sputter deposited amorphous silicon has more desirable electrical and optical properties when the material is prepared with low hydrogen concentration and monohydride bonding. Results of structural studies and hydrogen incorporation in amorphous silicon were discussed relative to the different models proposed for amorphous silicon

Nitrogen doped hydrogenatedamorphouscarbon thin films have been deposited by rf plasma-enhanced chemical vapor deposition using CH4 as the source of carbon and with different nitrogen flow rates (N2/CH4 gas ratios between 0 and 3), at 300 K. The dependence modifications of the optical and the structural properties on nitrogen incorporation were investigated using different spectroscopic techniques, such as, Raman spectroscopy, Fourier transform infrared spectroscopy, x-ray photoelectron spe...

Studies of amorphoushydrogenatedcarbon (a-C:H) film deposition revealed that methyl radicals are the precursor species responsible for the bulk mass deposition of the films, while the ions act to improve the mechanical properties. The films were deposited on Si(100) substrates both on the powered (negatively self-biased) and on the grounded electrodes from a methane rf plasma (13.56 MHz) at 68 to 70 mTorr and 300 to 370 K. The films produced on the powered electrode exhibited superior mechanical properties, such as high hardness. A mass spectrometer was used to identify neutral species and positive ions incident on the electrodes from the plasma, and also to measure ion energies. Methyl radicals were incident on the electrode surface with an estimated flux of 10 16 cm -2 s -1 , for a rf power of 50 W. Methyl radicals appear to be the dominant intermediates in the growth of the soft carbon polymer, and there is a remarkable decrease in deposition rate due to the introduction of NO, a radical scavenger. A novel pulsed biasing technique was used so that the role of ions in the plasma could be studied separately. It was found that the hardness of the films depends on the power supplied by the ions to the growing film surface (the time averaged difference between the plasma potential and the electrode potential), but not on the energy of individual ions. The pulsed biasing technique offers an efficient method to adjust the film hardness by independent control of the neutral radical and ion fluxes to the surface

Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphouscarbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenatedamorphouscarbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenatedamorphouscarbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has been inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. In conclusion, these findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H.

Amorphoushydrogenatedcarbon (a-C:H) films were studied with the objective of elucidating the nucleation and growth mechanisms, and the origin of their unique physical properties. The films were deposited onto Si(100) substrates both on the powered (negatively self-biased) and on the grounded electrodes from methane in an rf plasma (13.56 MHz) at 65 mTorr and 300 to 370 K. The films produced at the powered electrode exhibited superior mechanical properties, such as high hardness. A mass spectrometer was used to identify neutral species and positive ions incident on the electrodes from the plasma, and also to measure ion energies. The effect of varying ion energy flux on the properties of a-C:H films was investigated using a novel pulsed biasing technique. It was demonstrated that ions were not the dominant deposition species as the total ion flux measured was insufficient to account for the observed deposition rate. The interface between thin films of a-C:H and silicon substrates was investigated using angle resolved x-ray photoelectron spectroscopy. A silicon carbide layer was detected at the interface of a hard a-C:H film formed at the powered electrode. At the grounded electrode, where the kinetic energy is low, no interfacial carbide layer was observed. Scanning tunneling microscopy and high energy electron energy loss spectroscopy was used to investigate the initial stages of growth of a-C:H films. On graphite substrates, films formed at the powered electrode were observed to nucleate in clusters approximately 50 {Angstrom} in diameter, while at the grounded electrode no cluster formation was observed. 58 figs.

Abstract The synthesis, characterization and crystallization energetics of amorphous iron (II) carbonate (AFC) are reported. AFC may form as a precursor for siderite (FeCO3). The enthalpy of crystallization (DHcrys) of AFC is similar to that of amorphous magnesium carbonate (AMC) and more...

c0, c being the instantaneous concentration at a local point and c0, the average concentration of hydrogen in the hydrogenatedamorphous silicon. If the system is both incompressible and isotropic, the change in Helmholtz free energy due to fluctuations in the local concentration of hydrogen is given as. 122. Pramana – J.

Silicon Photonics is quickly proving to be a suitable interconnect technology for meeting the future goals of on-chip bandwidth and low power requirements. However, it is not clear how silicon photonics will be integrated into CMOS chips, particularly microprocessors. The issue of integrating photonic circuits into electronic IC fabrication processes to achieve maximum flexibility and minimum complexity and cost is an important one. In order to minimize usage of chip real estate, it will be advantageous to integrate in three-dimensions. Hydrogenatedamorphous silicon (a-Si:H) is emerging as a promising material for the 3-D integration of silicon photonics for on-chip optical interconnects. In addition, a-Si:H film can be deposited using CMOS compatible low temperature plasma-enhanced chemical vapor deposition (PECVD) process at any point in the fabrication process allowing maximum flexibility and minimal complexity. In this thesis, we demonstrate a-Si:H as a high performance alternate platform to crystalline silicon, enabling backend integration of optical interconnects in a hybrid photonic-electronic network-on-chip architecture. High quality passive devices are fabricated on a low-loss a-Si:H platform enabling wavelength division multiplexing schemes. We demonstrate a broadband all-optical modulation scheme based on free-carrier absorption effect, which can enable compact electro-optic modulators in a-Si:H. Furthermore, we comprehensively characterize the optical nonlinearities in a-Si:H and observe that a-Si:H exhibits enhanced nonlinearities as compared to crystalline silicon. Based on the enhanced nonlinearities, we demonstrate low-power four-wave mixing in a-Si:H waveguides enabling high speed all-optical devices in an a-Si:H platform. Finally, we demonstrate a novel data encoding scheme using thermal and all-optical tuning of silicon waveguides, increasing the spectral efficiency in an interconnect link.

This report discusses the results of probing the defect structure and bonding of hydrogenatedamorphous silicon films using both nuclear magnetic resonance (NMR) and electron spin resonance (ESR). The doping efficiency of boron in a-Si:H was found to be less than 1%, with 90% of the boron in a threefold coordinated state. On the other hand, phosphorus NMR chemical shift measurements yielded a ration of threefold to fourfold P sites of roughly 4 to 1. Various resonance lines were observed in heavily boron- and phosphorus-doped films and a-SiC:H alloys. These lines were attributed to band tail states on twofold coordinated silicon. In a-SiC:H films, a strong resonance was attributed to dangling bonds on carbon atoms. ESR measurements on low-pressure chemical-vapor-deposited (LPCVD) a-Si:H were performed on samples. The defect density in the bulk of the films was 10/sup 17//cc with a factor of 3 increase at the surface of the sample. The ESR spectrum of LPCVD-prepared films was not affected by prolonged exposure to strong light. Microcrystalline silicon samples were also examined. The phosphorus-doped films showed a strong signal from the crystalline material and no resonance from the amorphous matrix. This shows that phosphorus is incorporated in the crystals and is active as a dopant. No signal was recorded from the boron-doped films.

Nitrogen doped hydrogenatedamorphouscarbon thin films have been deposited by rf plasma-enhanced chemical vapor deposition using CH 4 as the source of carbon and with different nitrogen flow rates (N 2 /CH 4 gas ratios between 0 and 3), at 300 K. The dependence modifications of the optical and the structural properties on nitrogen incorporation were investigated using different spectroscopic techniques, such as, Raman spectroscopy, Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, ultraviolet-visible (UV-VIS) spectroscopy, electron spin resonance (ESR), photoluminescence (PL) and spectroscopic ellipsometry (SE). Raman spectroscopy and IR absorption reveal an increase in sp 2 -bonded carbon or a change in sp 2 domain size with increasing nitrogen flow rate. It is found that the configuration of nitrogen atoms incorporated into an amorphouscarbon network gradually changes from nitrogen atoms surrounded by three (σ bonded) to two (π bonded) neighboring carbons with increasing nitrogen flow rate. Tauc optical gap is reduced from 2.6 to 2.0 eV, and the ESR spin density and the peak-to-peak linewidth increase sharply with increasing nitrogen flow rate. Excellent agreement has been found between the measured SE data and modeled spectra, in which an empirical dielectric function of amorphous materials and a linear void distribution along the thickness have been assumed. The influence of nitrogen on the electronic density of states is explained based on the optical properties measured by UV-VIS and PL including nitrogen lone pair band. [copyright] 2001 American Institute of Physics

Silicon (1 0 0) has been gradually covered by amorphoushydrogenatedcarbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp2 carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp2 carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.

Films of hydrogenatedamorphouscarbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H 2 /CH 4 in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10 -4 to 6x10 -4 Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

Hydrogenatedamorphouscarbon (a-C:H) films were prepared by plasma enhanced chemical vapor deposition using methane (CH4) plus krypton (Kr) mixed atmosphere. The depositions were performed as function of the bias voltage and krypton partial pressure. The goal of this work was to study the influence of krypton gas on the physical properties of a-C:H films deposited on the cathode electrode. Krypton concentration up to 1.6 at. %, determined by Rutherford Back-Scattering, was obtained at high Kr partial pressure and bias of -120 V. The structure of the films was analyzed by means of optical transmission spectroscopy, multi-wavelength Raman scattering and Fourier Transform Infrared spectroscopy. It was verified that the structure of the films remains unchanged up to a concentration of Kr of about 1.0 at. %. A slight graphitization of the films occurs for higher concentration. The observed variation in the film structure, optical band gap, stress, and hydrogen concentration were associated mainly with the subplantation process of hydrocarbons radicals, rather than the krypton ion energy.

Hydrogenatedamorphouscarbon (a-C:H) films were prepared by plasma enhanced chemical vapor deposition using methane (CH 4 ) plus krypton (Kr) mixed atmosphere. The depositions were performed as function of the bias voltage and krypton partial pressure. The goal of this work was to study the influence of krypton gas on the physical properties of a-C:H films deposited on the cathode electrode. Krypton concentration up to 1.6 at. %, determined by Rutherford Back-Scattering, was obtained at high Kr partial pressure and bias of -120 V. The structure of the films was analyzed by means of optical transmission spectroscopy, multi-wavelength Raman scattering and Fourier Transform Infrared spectroscopy. It was verified that the structure of the films remains unchanged up to a concentration of Kr of about 1.0 at. %. A slight graphitization of the films occurs for higher concentration. The observed variation in the film structure, optical band gap, stress, and hydrogen concentration were associated mainly with the subplantation process of hydrocarbons radicals, rather than the krypton ion energy.

This book presents information on the following topoics: elements of the theory of amorphous semiconductors; electronic structure of alpha-SiH; fluctuation induced gap states in amorphoushydrogenated silicon; hydrogen on semiconductor surfaces; the influence of hydrogen on the defects and instabilities in hydrogenatedamorphous silicon; deuteron magnetic resonance in some amorphous semiconductors; formation of amorphous metals by solid state reactions of hydrogen with an intermetallic compound; NMR studies of the hydrides of disordered and amorphous alloys; neutron vibrational spectroscopy of disordered metal-hydrogen system; dynamical disorder of hydrogen in LaNi /SUB 5-y/ M /SUB y/ hydrides studied by quasi-elastic neutron scattering; recent studies of intermetallic hydrides; tritium in Pd and Pd /SUB 0.80/ Sg /SUB 0.20/ ; and determination of hydrogen concentration in thin films of absorbing materials

Full Text Available The electrochemical activity of the surface of Nitrogen-doped hydrogenatedamorphouscarbon thin films (a-CNH, N-doped DLC toward the inner sphere redox species is controllable by modifying the surface termination. At the oxygen plasma treated N-doped DLC surface (O-DLC, the surface functional groups containing carbon doubly bonded to oxygen (C=O, which improves adsorption of polar molecules, were generated. By oxidative treatment, the electron-transfer rate for dopamine (DA positively charged inner-sphere redox analyte could be improved at the N-doped DLC surface. For redox reaction of 2,4-dichlorophenol, which induces an inevitable fouling of the anode surface by forming passivating films, the DLC surfaces exhibited remarkably higher stability and reproducibility of the electrode performance. This is due to the electrochemical decomposition of the passive films without the interference of oxygen evolution by applying higher potential. The N-doped DLC film can offer benefits as the polarizable electrode surface with the higher reactivity and higher stability toward inner-sphere redox species. By making use of these controllable electrochemical reactivity at the O-DLC surface, the selective detection of DA in the mixed solution of DA and uric acid could be achieved.

In this study, we prepared hydrogenatedamorphouscarbon films on steel balls and Si substrates (steel ball- and Si substrate-films) with different deposition time, and discussed their carbon nanostructural evolutions and tribological behaviors. The steel ball-film structure started to be graphite-like structure and then gradually transformed into fullerene-like (FL) structure. The Si substrate-film structure began in FL structure and kept it through the thickness. The difference may be result from the competition between high starting substrate temperature after additional nitriding applied on the steel balls (its supply power is higher than that in the film deposition), and relaxation of compressive stress from energized ion bombardment in film deposition process. The FL structural film friction couples could achieve ultra-low friction in open air. In particular, the Si substrate-film with 3 h, against the steel ball-film with 2 h and 3 h, exhibited super-low friction (∼0.009) and superlong wear life (∼5.5 × 105 cycles). Our result could widen the superlubricity scope from previously high load and velocity, to middle load and velocity.

Methane (CH4) plasma was used to produce amorphoushydrogenatedcarbon (a-C:H) films by a single capacitively coupled radio frequency (RF) powered plasma system. The system consists of two parallel electrodes: the upper electrode is connected to 13.56 MHz RF power and the lower one is connected to the ground. Thin films were deposited on glass slides with different sizes and on silicon wafers. The influence of the plasma species on film characteristics was studied by changing the plasma parameters. The changes of plasma species during the deposition were investigated by optical emission spectroscopy (OES). The structural and optical properties were analyzed via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and UV-visible spectroscopy, and the thicknesses of the samples were measured by a profilometer. The sp3/sp2 ratio and the existing H atoms play a significant role in the determination of the chemical properties of thin films in the plasma. The film quality and deposition rate were both increased by raising the power and the flow rate.

Full Text Available In this study, wear behavior of amorphoushydrogenatedcarbon (a-C:H coating and tetrahedral amorphouscarbon (ta-C coating when sliding against various mating materials in base oil boundary lubrication condition is comparatively investigated to find out the optimal combinations of DLC/mating material and corresponding wear mechanism of both DLC coating. Tribological tests were performed in a cylinder-on-disc tribometer, Field Emission Scanning Electron Microscopy, Raman spectroscopy is used for characterization of ta-C and a-C:H worn surface. The results show that the specific wear rate of ta-C coating increases along with the hardness and roughness of mating material increases, while the specific wear rate of a-C:H coating increases together with an increment in the ID/IG ratio. It is concluded that for ta-C coating, local stress concentration-induced microfracture is the main wear mechanism in relative high wear scenario, along with minor graphitization-induced wear which prevails in low wear scenario. On the other hand, a-C:H coating showed that simultaneous generation and removal of the graphitized layer on the contact surface is the predominant wear mechanism.

been found to be having a lot of technological applica- tions. The properties of these amorphouscarbons sensi- tively depend on the relative concentration of sp3 and sp2 hybridized carbons. The resulting amorphous materials are variously referred to as tetrahedral amorphouscarbon. (ta-C), amorphouscarbon (a-C), ...

Full Text Available The compositions and bonding states of the amorphoushydrogenatedcarbon films at various thicknesses were evaluated via near-edge X-ray absorption fine-structure (NEXAFS and elastic recoil detection analysis combined with Rutherford backscattering spectrometry. The absolute carbon sp2 contents were determined to decrease to 65% from 73%, while the hydrogen contents increase from 26 to 33 at.% as the film thickness increases. In addition, as the film thickness increases, the π⁎ (C=C, σ⁎ (C–H, σ⁎ (C=C, and σ⁎ (C≡C bonding states were found to increase, whereas the π⁎ (C≡C and σ⁎ (C–C bonding states were observed to decrease in the NEXAFS spectra. Consequently, the film thickness is a key factor to evaluate the composition and bonding state of the films.

A novel solar cell architecture made completely from the earth abundant elements silicon and carbon has been developed. Hydrogenatedamorphous silicon (aSi:H), rather than crystalline silicon, is used as the active material due to its high absorption through a direct band gap of 1.7eV, well matched to the solar spectrum to ensure the possibility of improved cells in this architecture with higher efficiencies. The cells employ a Schottky barrier design wherein the amorphous silicon absorber la...

Amorphous and nanocrystalline carbon films possess special chemical and physical properties such as high chemical inertness, diamond-like properties, and favorable tribological proprieties. The materials usually consist of graphite and diamond microstructures and thus possess properties that lie between the two. Amorphous and nanocrystalline carbon films can exist in different kinds of matrices and are usually doped with a large amount of hydrogen. Thus, carbon films can be classified as polymer-like, diamond-like, or graphite-like based on the main binding framework. In order to characterize the structure, either direct bonding characterization methods or the indirect bonding characterization methods are employed. Examples of techniques utilized to identify the chemical bonds and microstructure of amorphous and nanocrystalline carbon films include optical characterization methods such as Raman spectroscopy, Ultra-violet (UV) Raman spectroscopy, and infrared spectroscopy, electron spectroscopic and microscopic methods such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, transmission electron microscopy, and electron energy loss spectroscopy, surface morphology characterization techniques such as scanning probe microscopy (SPM) as well as other characterization methods such as X-ray reflectivity and nuclear magnetic resonance. In this review, the structures of various types of amorphouscarbon films and common characterization techniques are described

We have studied hydrogen-passivated amorphouscarbon nanostructures with semiempirical molecular orbital theory in order to provide an understanding of the factors that affect their electronic properties. Amorphous structures were first constructed using periodic calculations in a melt/quench protocol. Pure periodic amorphouscarbon structures and their counterparts doped with nitrogen and/or oxygen feature large electronic band gaps. Surprisingly, descriptors such as the elemental composition and the number of sp(3)-atoms only influence the electronic structure weakly. Instead, the exact topology of the sp(2)-network in terms of effective conjugation defines the band gap. Amorphouscarbon nanodots of different structures and sizes were cut out of the periodic structures. Our calculations predict the occurrence of localized electronic surface states, which give rise to interesting effects such as amphoteric reactivity and predicted optical band gaps in the near-UV/visible range. Optical and electronic gaps display a dependence on particle size similar to that of inorganic colloidal quantum dots.

The influence of radio-frequency (RF) power on the structure and gas permeation through amorphoushydrogenatedcarbon films deposited on cylindrical polyethylene terephthalate (PET) samples is investigated. The results show that a higher radio-frequency power leads to a smaller sp 3 /sp 2 value but produces fewer defects with smaller size. The permeability of PET samples decreases significantly after a-C:H deposition and the RF only exerts a small influence. However, the coating uniformity, color, and wettability of the surface are affected by the RF power. A higher RF power results in to better uniformity and it may be attributed to the combination of the high-density plasma and sample heating.

Hydrogenatedamorphouscarbon thin films were deposited by RF plasma polymerization in argon/n-hexane gas mixture on polyethylene terephthalate (PET) foils. It was found that such deposited films may significantly improve the barrier properties of PET. It was demonstrated that the principal parameter that influences barrier properties of such deposited films towards oxygen and water vapor is the density of the coatings. Moreover, it was shown that for achieving good barrier properties it is advantageous to deposit coatings with very low thickness. According to the presented results, optimal thickness of the coating should not be higher than several tens of nm. - Highlights: • a-C:H films were prepared by plasma polymerization in Ar/n-hexane atmosphere. • Barrier properties of coatings are dependent on their density and thickness. • Highest barrier properties were observed for films with thickness 15 nm.

The quality of the a-C:H films was particularly correlated with the mixed ratio of methane/argon plasma. For a constant supply of energy and flowing rate, the optical emission from H α intensity linearly increased with the addition of methane in argon plasma, while that from intensities of radiation of diatmoic radicals (CH*and C 2 *) exponentially decreased. For the a-C:H films, the added methane in argon plasma tended to raise the quantity of hydrogenatedcarbon or sp 3 C-H structure, which exponentially decreased the nano-hardness and friction coefficient of the films. In contrast, the electric resistance of the films enlarged dramatically with the increase of the methane content in argon plasma. It is therefore advantageous to balance the mechanical properties and electrical resistance of the a-C:H film by adjusting plasma composition in the course of the film-growing process.

The photo-response behaviour of Amorphous Silicon Position Detectors (ASPDs) under prolonged illumination with a 681 nm diode-laser and a 633 nm He-Ne laser is presented. Both direct and inverse Staebler-Wronski effects are observed.

in nanotubes and sp3 rich amorphouscarbons for their application in field emission, device application, etc in- vestigations on sp2 rich amorphouscarbon forms are very few. Though DLC films have potential application in field emission (FE) due to their low threshold voltage, the carbon centres, which are believed to play ...

We report studies of the interactions of quantified deuterium (hydrogen) atom beams with hard amorphoushydrogenatedcarbon films at a substrate temperature of ˜330 K in an ultrahigh-vacuum chamber. The modification/erosion of a-C:H (a-C:D) films was monitored in situ by ellipsometry in real time. By interpreting the ellipsometric information and combining it with measurements of the absolute D areal density changes in the a-C:H (a-C:D) films by ion beam analysis as a function of D (H) atom fluence, we are able to distinguish three sequential stages of D interaction with hard a-C:H films. The first stage is replacement of bonded hydrogen by deuterium up to an areal density of ˜5×1015 D cm-2 to a depth of ˜1.4 nm from the surface. This phase is complete after a deuterium fluence of ≈2×1018 cm-2. The effective cross section for isotopic exchange of H with D atoms for the a-C:H layer is found to be σ =2.0×10-18 cm2, and is close to the cross section for H abstraction from a carbon surface. This may indicate that H abstraction by D from the a-C:H surface is the rate limiting step for isotope exchange in this situation. Hydrogen replacement is followed by creation of additional C-D bonds in the near-surface region and increases the D areal density by about 2.5×1015 D cm-2. By ellipsometry this process can be observed as the formation of a soft a-C:D layer on top of the hard a-C:H bulk film, with the soft layer extending about 1.4 nm from the surface. This stage is complete after a deuterium fluence of about 2×1019 cm-2. Subsequently, steady-state erosion of the a-C:H film takes place. Here, a soft a-C:D layer with roughly constant thickness (˜1.4 nm) remains on the hard a-C:H substrate and is dynamically reformed as the underlying hard a-C:H film becomes thinner. A similar sequence of processes takes place at a substrate temperature of 650 K, albeit at a much faster rate.

Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

Biomaterial surfaces are at high risk for initial microbial colonization, persistence, and concomitant infection. The rationale of this study was to assess the initial adhesion on novel implant surfaces of Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans upon incubation. The tested samples were 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) samples with nitrogen-doped hydrogenatedamorphouscarbon (a-C:H:N) coating (A) and 3Y-TZP samples coated with ceria-stabilized zirconia-based (Ce-TZP) composite and a-C:H:N (B). Uncoated 3Y-TZP samples (C) and bovine enamel slabs (BES) served as controls. Once the surface was characterized, the adherent microorganisms were quantified by estimating the colony-forming units (CFUs). Microbial vitality was assessed by live/dead staining, and microbial-biomaterial surface topography was visualized by scanning electron microscopy (SEM). Overall, A and B presented the lowest CFU values for all microorganisms, while C sheltered significantly less E. faecalis, P. aeruginosa, and C. albicans than BES. Compared to the controls, B demonstrated the lowest vitality values for E. coli (54.12 %) and C. albicans (67.99 %). Interestingly, A (29.24 %) exhibited higher eradication rates for S. aureus than B (13.95 %). Within the limitations of this study, a-C:H:N-coated 3Y-TZP surfaces tended to harbor less initially adherent microorganisms and selectively interfered with their vitality. This could enable further investigation of the new multi-functional zirconia surfaces to confirm their favorable antimicrobial properties in vivo.

Many MEMS devices are based on polysilicon because of the current availability of surface micromachining technology. However, polysilicon is not the best choice for devices where extensive sliding and/or thermal fields are applied due to its chemical, mechanical and tribological properties. In this work, we investigated the mechanical properties of three new materials for MEMS/NEMS devices: silicon carbide (SiC) from Case Western Reserve University (CWRU), ultrananocrystalline diamond (UNCD) from Argonne National Laboratory (ANL), and hydrogen-free tetrahedral amorphouscarbon (ta-C) from Sandia National Laboratories (SNL). Young's modulus, characteristic strength, fracture toughness, and theoretical strength were measured for these three materials using only one testing methodology - the Membrane Deflection Experiment (MDE) developed at Northwestern University. The measured values of Young's modulus were 430GPa, 960GPa, and 800GPa for SiC, UNCD, and ta-C, repectively. Fracture toughness measurments resulted in values of 3.2, 4.5, and 6.2 MPa x m{sup 1/2}, respectively. The strengths were found to follow a Weibull distribution but their scaling was found to be controlled by different specimen size parameters. Therefore, a cross comparison of the strengths is not fully meaningful. We instead propose to compare their theoretical strengths as determined by employing Novozhilov fracture criterion. The estimated theoretical strength for SiC is 10.6GPa at a characteristic length of 58nm, for UNCD is 18.6GPa at a characteristic length of 37nm, and for ta-C is 25.4GPa at a characteristic length of 38nm. The techniques used to obtained these results as well as microscopic fractographic analyses are summarized in the article. We also highlight the importance of characterizing mechanical properties of MEMS materials by means of only one simple and accurate experimental technique.

Full Text Available We report about properties of carbon layers doped with Er3+ ions fabricated by Plasma Assisted Chemical Vapor Deposition (PACVD and by sputtering on silicon or glass substrates. The structure of the samples was characterized by X-ray diffraction and their composition was determined by Rutherford Backscattering Spectroscopy and Elastic Recoil Detection Analysis. The Absorbance spectrum was taken in the spectral range from 400 nm to 600 nm. Photoluminescence spectra were obtained using two types of Ar laser (λex=514.5 nm, lex=488 nm and also using a semiconductor laser (λex=980 nm. Samples fabricated by magnetron sputtering exhibited typical emission at 1530 nm when pumped at 514.5 nm.

Full Text Available Increasing environmental awareness and demands for lowering energy consumptions are strong driving forces behind the development of the vehicles of tomorrow. Without the advances of lubricant chemistry and adequate lubricant formulation, expansion of modern engines would not have been possible. Considering environmental awareness factors as compared to mineral oils, vegetal oil based biolubricants are renewable, biodegradable, non-toxic and have a least amount of greenhouse gases. Furthermore, improvement in engine performance and transmission components, which were impossible to achieve by applying only lubricants design, is now possible through diamond like carbon (DLC coatings. DLC coatings exhibit brilliant tribological properties, such as good wear resistance and low friction. In this regard, tribological performance of a-C: H DLC coating when lubricated with Canola vegetal oil has been investigated by the help of a ball-on-flat geometry. Experimental results demonstrated that the a-C: H DLC coating exhibited better performance with Canola oil in terms of friction and wear as compared to the uncoated materials. Large amount of polar components in the Canola oil significantly improved the tribological properties of the a-C:H coating. Thus, usage of a-C: H DLC coating with Canola oil in the long run may have a positive impact on engine life.

A method for joining or repairing boron nitride nanotubes (BNNTs). In joining BNNTs, the nanotube structure is modified with amorphouscarbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures. In repairing BNNTs, the damaged site of the nanotube structure is modified with amorphouscarbon deposited by controlled electron beam irradiation to form well bonded hybrid a-C/BNNT structures at the damage site.

This invention relates to hydrogenatedamorphous silicon produced by thermally decomposing silano (SiH.sub.4) or other gases comprising H and Si, at elevated temperatures of about 1700.degree.-2300.degree. C., and preferably in a vacuum of about 10.sup.-8 to 10.sup.-4 torr, to form a gaseous mixture of atomic hydrogen and atomic silicon, and depositing said gaseous mixture onto a substrate outside said source of thermal decomposition to form hydrogenatedamorphous silicon.

Hydrogenatedamorphous silicon is produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, at elevated temperatures of about 1700 to 2300/sup 0/C, in a vacuum of about 10/sup -8/ to 10/sup -4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate to form hydrogenatedamorphous silicon.

Small angle x-ray scattering (SAXS) and deuterium secondary-ion-mass spectrometry (DSIMS) studies of the microstructure and hydrogen dynamics in undoped rf-sputter-deposited (RFS) and undoped and boron-doped electron-cyclotron-resonance-deposited (ECR) hydrogenatedamorphous silicon carbides (a-Si1-xCx:H) are described. In the RFS carbides with xcarbides with xBoron doping of the ECR carbides also reduced the bulklike Si-bonded H content, suggesting that it induces nanovoids, consistent with the observed suppression of long-range motion of most of the H and D atoms. However, a small fraction of the H atoms appeared to undergo fast diffusion, reminiscent of the fast diffusion in B-doped a-Si:H.

A process for making a hydrogenatedcarbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenatedcarbon material. A hydrogenatedcarbon material including a hydrogencarbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

The application of diamond-like carbon (DLC) coatings on automotive components is emerging as a favorable strategy to address the recent challenges in the industry. DLC coatings can effectively lower the coefficient of friction (CoF) and wear rate of engine components, thereby improving their fuel efficiency and durability. The lubrication of ferrous materials can be enhanced by a large amount of unsaturated and polar components of oils. Therefore, the interaction between nonferrous coatings (e.g., DLC) and vegetable oil should be investigated. A ball-on-plate tribotester was used to run the experiments. Stainless steel plates coated with amorphoushydrogenated (a-C:H) DLC and hydrogen-free tetrahedral (ta-C) DLC that slide against 440C stainless steel ball were used to create a ball-on-plate tribotester. The wear track was investigated through scanning electron microscopy. Energy dispersive and X-ray photoelectron spectroscopies were used to analyze the tribofilm inside the wear track. Raman analysis was performed to investigate the structural changes in the coatings. At high temperatures, the CoF in both coatings decreased. The wear rate, however, increased in the a-C:H but decreased in the ta-C DLC-coated plates. The CoF and the wear rate (coated layer and counter surface) were primarily influenced by the graphitization of the coating. Tribochemical films, such as polyphosphate glass, were formed in ta-C and acted as protective layers. Therefore, the wear rate of the ta-C DLC was lower than that of the-C:H DLC.

We demonstrate optical parametric amplification operating at GHz-rates at telecommunications wavelengths using a hydrogenatedamorphous silicon waveguide through the nonlinear optical process of four-wave mixing. We investigate how the parametric amplification scales with repetition rate. The ability to achieve amplification at GHz-repetition rates shows hydrogenatedamorphous silicon’s potential for telecommunication applications and a GHz-rate optical parametric oscillator. (paper)

In this paper we describe a method to generate amorphous structures with arbitrary structural constraints. This method employs the simulated annealing algorithm to minimize a simple yet carefully tailored cost function (CF). The cost function is composed of two parts: a simple harmonic approximation for the energy-related terms and a cost that penalizes configurations that do not have atoms in the desired coordinations. Using this approach, we generated a set of amorphouscarbon structures spawning nearly all the possible combinations of sp, sp(2) and sp(3) hybridizations. The bulk moduli of this set of amorphouscarbons structures was calculated using Brenner's potential. The bulk modulus strongly depends on the mean coordination, following a power-law behavior with an exponent ν = 1.51 ± 0.17. A modified cost function that segregates carbon with different hybridizations is also presented, and another set of structures was generated. With this new set of amorphous materials, the correlation between the bulk modulus and the mean coordination weakens. The method proposed can be easily modified to explore the effects on the physical properties of the presence of hydrogen, dangling bonds, and structural features such as carbon rings.

We have generated a model of hydrogenatedamorphous silicon by first-principles molecular dynamics. Our results are in good agreement with the available experimental data and provide new insight into the microscopic structure of this material. The calculation lends support to models in which monohydride complexes are prevalent, and indicates a strong tendency of hydrogen to form small clusters.

We have generated a computer model of hydrogenatedamorphous silicon by first-principles molecular dynamics. Our results are in good agreement with the available experimental data, and provide new insight into the microscopic structure of this material. This should lead to a better understanding of the hydrogenation process. 13 refs., 2 figs.

We have studied the evolution of the structure of intrinsic and doped hydrogenatedamorphous silicon films exposed to a hydrogen plasma. For this purpose, we combine in situ spectroscopic ellipsometry and secondary ion mass spectrometry measurements. We show that hydrogen diffuses faster in boron-doped hydrogenatedamorphous silicon than in intrinsic samples, leading to a thicker subsurface layer from the early stages of hydrogen plasma exposure. At longer times, hydrogen plasma leads to the formation of a microcrystalline layer via chemical transport, but there is no evidence for crystallization of the a-Si:H substrate. Moreover, we observe that once the microcrystalline layer is formed, hydrogen diffuses out of the sample

Amorphous conducting carbon films deposited over quartz substrates were analysed using X-ray diffraction and AFM technique. X-ray diffraction data reveal disorder and roughness in the plane of graphene sheet as compared to that of graphite. This roughness increases with decrease in preparation temperature. The AFM ...

Stretched exponential relaxation has been observed in various phenomena of hydrogenatedamorphous silicon (a-Si:H) and hydrogenated polymorphous silicon (pm-Si:H). As an example, we take light-induced defect creation in a-Si:H and pm-Si:H, in which defect-creation process and defect-annihilation process via hydrogen movement play important roles. We have performed the Monte Carlo simulation for hydrogen movement. Hydrogen movement exhibits anomalous diffusion. In our model of light-induced defect creation in a-Si:H, a pair of two types of dangling bonds, i.e., a normal dangling bond and a hydrogen-related dangling bond, that is a dangling bond having hydrogen in the nearby site, are created under illumination, and hydrogen dissociated from the hydrogen-related dangling bond terminates a normal dangling bond via hydrogen movement. The amorphous network reflects on the dispersive parameter of the stretched exponential function in the light-induced defect creation. We discuss this issue, taking into account the difference in the amorphous network between a-Si:H and pm-Si:H (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Highlights: • We tested a-C:H and ta-C DLC coatings as a function of temperature. • Jatropha oil contains large amounts of polar components that enhanced the lubricity of coatings. • CoF decreases with increasing temperature for both contacts. • Wear rate increases with increasing temperature in a-C:H and decreases in ta-C DLC. • At high temperature, ta-C coatings confer more protection than a-C:H coatings. - Abstract: The application of diamond-like carbon (DLC) coatings on automotive components is emerging as a favorable strategy to address the recent challenges in the industry. DLC coatings can effectively lower the coefficient of friction (CoF) and wear rate of engine components, thereby improving their fuel efficiency and durability. The lubrication of ferrous materials can be enhanced by a large amount of unsaturated and polar components of oils. Therefore, the interaction between nonferrous coatings (e.g., DLC) and vegetable oil should be investigated. A ball-on-plate tribotester was used to run the experiments. Stainless steel plates coated with amorphoushydrogenated (a-C:H) DLC and hydrogen-free tetrahedral (ta-C) DLC that slide against 440C stainless steel ball were used to create a ball-on-plate tribotester. The wear track was investigated through scanning electron microscopy. Energy dispersive and X-ray photoelectron spectroscopies were used to analyze the tribofilm inside the wear track. Raman analysis was performed to investigate the structural changes in the coatings. At high temperatures, the CoF in both coatings decreased. The wear rate, however, increased in the a-C:H but decreased in the ta-C DLC-coated plates. The CoF and the wear rate (coated layer and counter surface) were primarily influenced by the graphitization of the coating. Tribochemical films, such as polyphosphate glass, were formed in ta-C and acted as protective layers. Therefore, the wear rate of the ta-C DLC was lower than that of the-C:H DLC

Highlights: • We tested a-C:H and ta-C DLC coatings as a function of temperature. • Jatropha oil contains large amounts of polar components that enhanced the lubricity of coatings. • CoF decreases with increasing temperature for both contacts. • Wear rate increases with increasing temperature in a-C:H and decreases in ta-C DLC. • At high temperature, ta-C coatings confer more protection than a-C:H coatings. - Abstract: The application of diamond-like carbon (DLC) coatings on automotive components is emerging as a favorable strategy to address the recent challenges in the industry. DLC coatings can effectively lower the coefficient of friction (CoF) and wear rate of engine components, thereby improving their fuel efficiency and durability. The lubrication of ferrous materials can be enhanced by a large amount of unsaturated and polar components of oils. Therefore, the interaction between nonferrous coatings (e.g., DLC) and vegetable oil should be investigated. A ball-on-plate tribotester was used to run the experiments. Stainless steel plates coated with amorphoushydrogenated (a-C:H) DLC and hydrogen-free tetrahedral (ta-C) DLC that slide against 440C stainless steel ball were used to create a ball-on-plate tribotester. The wear track was investigated through scanning electron microscopy. Energy dispersive and X-ray photoelectron spectroscopies were used to analyze the tribofilm inside the wear track. Raman analysis was performed to investigate the structural changes in the coatings. At high temperatures, the CoF in both coatings decreased. The wear rate, however, increased in the a-C:H but decreased in the ta-C DLC-coated plates. The CoF and the wear rate (coated layer and counter surface) were primarily influenced by the graphitization of the coating. Tribochemical films, such as polyphosphate glass, were formed in ta-C and acted as protective layers. Therefore, the wear rate of the ta-C DLC was lower than that of the-C:H DLC.

The ubiquitous low-energy excitations, known as two-level tunneling systems (TLSs), are one of the universal phenomena of amorphous solids. Low temperature elastic measurements show that e-beam amorphous silicon (a-Si) contains a variable density of TLSs which diminishes as the growth temperature reaches 400 °C. Structural analyses show that these a-Si films become denser and more structurally ordered. We conclude that the enhanced surface energetics at a high growth temperature improved the amorphous structural network of e-beam a-Si and removed TLSs. This work obviates the role hydrogen was previously thought to play in removing TLSs in the hydrogenated form of a-Si and suggests it is possible to prepare "perfect" amorphous solids with "crystal-like" properties for applications.

Films of hydrogenatedamorphouscarbon (a-C:H) were deposited using one source of microwave plasma with magnetic field (type ECR), using mixtures of H{sub 2}/CH{sub 4} in relationship of 80/20 and 95/05 as precursory gases, with work pressures of 4X10{sup -4} to 6x10{sup -4} Torr and an incident power of the discharge of microwaves with a constant value of 400 W. It was analyzed the influence among the properties of the films, as the deposit rate, the composition and the bonding types, and the deposit conditions, such as the flow rates of the precursory gases and the polarization voltage of the sample holders. (Author)

At the beginning of this project, thin film amorphous alloy membranes were considered a nascent but promising new technology for industrial-scale hydrogen gas separations from coal- derived syngas. This project used a combination of theoretical modeling, advanced physical vapor deposition fabricating, and laboratory and gasifier testing to develop amorphous alloy membranes that had the potential to meet Department of Energy (DOE) targets in the testing strategies outlined in the NETL Membrane Test Protocol. The project is complete with Southwest Research Institute® (SwRI®), Georgia Institute of Technology (GT), and Western Research Institute (WRI) having all operated independently and concurrently. GT studied the hydrogen transport properties of several amorphous alloys and found that ZrCu and ZrCuTi were the most promising candidates. GT also evaluated the hydrogen transport properties of V, Nb and Ta membranes coated with different transition-metal carbides (TMCs) (TM = Ti, Hf, Zr) catalytic layers by employing first-principles calculations together with statistical mechanics methods and determined that TiC was the most promising material to provide catalytic hydrogen dissociation. SwRI developed magnetron coating techniques to deposit a range of amorphous alloys onto both porous discs and tubular substrates. Unfortunately none of the amorphous alloys could be deposited without pinhole defects that undermined the selectivity of the membranes. WRI tested the thermal properties of the ZrCu and ZrNi alloys and found that under reducing environments the upper temperature limit of operation without recrystallization is ~250 °C. There were four publications generated from this project with two additional manuscripts in progress and six presentations were made at national and international technical conferences. The combination of the pinhole defects and the lack of high temperature stability make the theoretically identified most promising candidate amorphous alloys

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.

Computing with resistive-switching (memristive) memory devices has shown much recent progress and offers an attractive route to circumvent the von-Neumann bottleneck, i.e. the separation of processing and memory, which limits the performance of conventional computer architectures. Due to their good scalability and nanosecond switching speeds, carbon-based resistive-switching memory devices could play an important role in this respect. However, devices based on elemental carbon, such as tetrahedral amorphouscarbon or ta-C, typically suffer from a low cycling endurance. A material that has proven to be capable of combining the advantages of elemental carbon-based memories with simple fabrication methods and good endurance performance for binary memory applications is oxygenated amorphouscarbon, or a-CO x . Here, we examine the memristive capabilities of nanoscale a-CO x devices, in particular their ability to provide the multilevel and accumulation properties that underpin computing type applications. We show the successful operation of nanoscale a-CO x memory cells for both the storage of multilevel states (here 3-level) and for the provision of an arithmetic accumulator. We implement a base-16, or hexadecimal, accumulator and show how such a device can carry out hexadecimal arithmetic and simultaneously store the computed result in the self-same a-CO x cell, all using fast (sub-10 ns) and low-energy (sub-pJ) input pulses.

Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.

Carbon is emerging as a material with great potential for photovoltaics (PV). However, the amorphous form (a-C) has not been studied in detail as a PV material, even though it holds similarities with amorphous Silicon (a-Si) that is widely employed in efficient solar cells. In this work, we correlate the structure, bonding, stoichiometry, and hydrogen content of a-C with properties linked to PV performance such as the electronic structure and optical absorption. We employ first-principles molecular dynamics and density functional theory calculations to generate and analyze a set of a-C structures with a range of densities and hydrogen concentrations. We demonstrate that optical and electronic properties of interest in PV can be widely tuned by varying the density and hydrogen content. For example, sunlight absorption in a-C films can significantly exceed that of a same thickness of a-Si for a range of densities and H contents in a-C. Our results highlight promising features of a-C as the active layer material of thin-film solar cells.

Thick amorphouscarbon films were deposited by the Magnets-in-Motion (M-M) rf linear hollow cathode at varying acetylene contents in Ar in a hybrid PVD/PE-CVD process directly on glass substrates. The hollow cathode plates manufactured from graphite were used as the PVD target. The measurements show that the films can reach thickness of up to 50 μm at deposition rates of up to 2.5 μm/min. Scratch test measurements confirm that well adhering films several μm thick can be achieved at C2H2 contents of up to 0.5%.

The physico chemical characterization of hydrogenatedamorphous silicon thin films (0,5 to 2 μm thick) makes use of nuclear microanalysis for quantitative determination and depth profiling of the elements hydrogen, oxygen, argon and carbon. Concerning the methods, performances of the hydrogen analysis using the 1 H( 15 N, αγ) nuclear reaction are presented emphasizing the precision and the analytical consequences of the interaction ion-material. For charged particles data processing (mainly Rutherford backscattering) computer treatments have been developed either for concentration profile obtention as for spectra prediction of given material configurations. The essential results concerning hydrogenated silicon prepared by RF sputtering are on one hand the correlation between the oxygen incorporation and the beam-induced hydrogen effusion and in the other hand the role of the substrate in the impurities incorporation. From the study of the elaboration conditions of the material a tentative interpretation is made for the incorporation and the role of oxygen [fr

Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetics and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of three- and four-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetics of PLD growth results in films becoming more ''diamondlike,'' i.e., increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film. (c) 2000 The American Physical Society.

Dozens of models are investigated by the first-principles calculations to simulate the interactions of an atomic hydrogen with a defect-free random network of amorphous SiO2 (a-SiO2) and oxygen vacancies. A wide variety of stable configurations are discovered due to the disorder of a-SiO2, and their structures, charges, magnetic moments, spin densities, and density of states are calculated. The atomic hydrogen interacts with the defect-free a-SiO2 in positively or negatively charged state, and produces the structures absent in crystalline SiO2. It passivates the neutral oxygen vacancies and generates two neutral hydrogenated E‧ centers with different Si dangling bond projections. Electron spin resonance parameters, including Fermi contacts, and g-tensors, are calculated for these centers. The atomic hydrogen interacts with the positive oxygen vacancies in dimer configuration, and generate four different positive hydrogenated defects, two of which are puckered like the Eγ‧ centers. This research helps to understand the interactions between an atomic hydrogen, and defect-free a-SiO2 and oxygen vacancies, which may generate the hydrogen-complexed defects that play a key role in the degeneration of silicon/silica-based microelectronic devices.

A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.

The present work is devoted to the study of some optical properties of hydrogenatedamorphous silicon (a-Si:H) thin films prepared by radio-frequency cathodic sputtering technique. It is essentially focused on investigating separately the effects of increasing partial hydrogen pressure during the deposition stage, and the effects of post deposition thermal annealing on the main optical parameters of the deposited layers (refraction index, optical gap Urbach energy, etc.). We show that low hydrogen pressures allow a saturation of the dangling bonds in the material, while high pressures lead to the creation of new defects. We also show that thermal annealing under moderate temperatures allows a good improvement of the structural quality of deposited films. (author)

Focused ion beam-secondary ion mass spectrometry (FIB-SIMS) with 20 nm spatial resolution has been used to analyze amorphous fluorinated carbon thin films, deposited by plasma assisted chemical vapor deposition (PACVD), at micro- to nano-scale. Mass spectra and ion imaging of film surface were acquired and the presence and distribution of contaminants were investigated. Surface images show the secondary ion distribution for F(-), CH(-), CF(-). A change in size and topology of fluorine-rich areas is correlated with film hardness and with microstructure transition from diamond-like to polymer-like, as indicated by infrared and Raman spectroscopies. Based on the surface distributions of CF(-) and CH(-) and on the vibrational spectroscopy results, a mechanism of fluorine substitution for hydrogen and an attempt to explain the film structure and microstructure is proposed.

Silicon-based materials present a high potential for dental implant applications, since silicon has been proven necessary for the correct bone formation in animals and humans. Notably, the addition of silicon is effective to enhance the bioactivity of hydroxyapatite and other biomaterials. The present work aims to expand the knowledge of the role exerted by hydrogen in the biological interaction of silicon-based materials, comparing two hydrogenatedamorphous silicon coatings, with different hydrogen content, as means to enhance soft tissue cell adhesion. To accomplish this task, the films were produced by plasma enhanced chemical vapor deposition (PECVD) on titanium substrates and their surface composition and hydrogen content were analyzed by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectrophotometry (FTIR) respectively. The surface energy and roughness were measured through optical contact angle analysis (OCA) and high-resolution mechanical profilometry respectively. Coated surfaces showed a slightly lower roughness, compared to bare titanium samples, regardless of the hydrogen content. The early cell responses of human keratinocytes and fibroblasts were tested on the above mentioned surface modifications, in terms of cell adhesion, viability and morphometrical assessment. Films with lower hydrogen content were endowed with a surface energy comparable to the titanium surfaces. Films with higher hydrogen incorporation displayed a lower surface oxidation and a considerably lower surface energy, compared to the less hydrogenated samples. As regards mean cell area and focal adhesion density, both a-Si coatings influenced fibroblasts, but had no significant effects on keratinocytes. On the contrary, hydrogen-rich films increased manifolds the adhesion and viability of keratinocytes, but not of fibroblasts, suggesting a selective biological effect on these cells.

Growth mechanism for synthesizing PVD based Graphene using AmorphousCarbon, catalyzed by Copper is investigated in this work. Different experiments with respect to AmorphousCarbon film thickness, annealing time and temperature are performed for the investigation. Copper film stress and its effect on hydrogen diffusion through the film grain boundaries are found to be the key factors for the growth mechanism, and supported by our Finite Element Modeling. Low temperature growth of Graphene is achieved and the proposed growth mechanism is found to remain valid at low temperatures.

Hydrogen diffusion is technologically critical to the processing of amorphous Si for solar cell applications. It is shown that this diffusion belongs to a broad class of dielectric relaxation mechanisms which were first studied by Kohlrausch in 1847. A microscopic theory of the Kohlrausch relaxation constant [beta][sub K] is also constructed. This theory explains the values of [beta] observed in many electronic, molecular and polymeric relaxation processes. It is based on two novel concepts: Wiener sausages, from statistical mechanics, and the magic wand, from axiomatic set theory

Firsts results on particle detection using a novel silicon pixel detector are presented. The sensor consists of an array of 48 square pixels with 380 μm pitch based on a n–i–p hydrogenatedamorphous silicon (a-Si:H) film deposited on top of a VLSI chip. The deposition was performed by VHF-PECVD, which enables high rate deposition up to 2 nm/s. Direct particle detection using beta particles from 63Ni and 90Sr sources was performed.

The article gives a comprehensive overview of hydrogen storage in carbon nanostructures, including experimental results and theoretical calculations. Soon after the discovery of carbon nanotubes in 1991, different research groups succeeded in filling carbon nanotubes with some elements, and, therefore, the question arose of filling carbon nanotubes with hydrogen by possibly using new effects such as nano-capillarity. Subsequently, very promising experiments claiming high hydrogen storage capacities in different carbon nanostructures initiated enormous research activity. Hydrogen storage capacities have been reported that exceed the benchmark for automotive application of 6.5 wt% set by the U.S. Department of Energy. However, the experimental data obtained with different methods for various carbon nanostructures show an extreme scatter. Classical calculations based on physisorption of hydrogen molecules could not explain the high storage capacities measured at ambient temperature, and, assuming chemisorption of hydrogen atoms, hydrogen release requires temperatures too high for technical applications. Up to now, only a few calculations and experiments indicate the possibility of an intermediate binding energy. Recently, serious doubt has arisen in relation to several key experiments, causing considerable controversy. Furthermore, high hydrogen storage capacities measured for carbon nanofibers did not survive cross-checking in different laboratories. Therefore, in light of today's knowledge, it is becoming less likely that at moderate pressures around room temperature carbon nanostructures can store the amount of hydrogen required for automotive applications.

A novel amorphouscarbon-carbon composite has been developed using carbon black dispersed in carbonized phenolic resin matrix in order to avoid Wigner energy problem associated with graphite. The as prepared sample showed a density of 1320 kg m-3. This has been further densified by resin impregnation and chemical vapour infiltration. The effect of processing parameters on final density (1517 kg m-3) has been investigated. This composite possesses the compressive strength of 65 Mpa, coefficient of thermal expansion of 3 × 10-6 K-1 and the specific heat of 1.2 J g-1 K-1. This novel composite was subjected to 145 MeV Ne+6 heavy ion irradiation at different doses. The highest dose was kept at 3 × 10-4 dpa. The stored energy in the composite was found to be 212 J g-1 at the highest dose of irradiation, which is much below than that of graphite. The composite remained amorphous after irradiation as confirmed by X-ray diffraction.

Hydrogenatedamorphous silicon is a relatively new material with device applications including photovoltaics. Intrinsic and light-induced electronic defects reduce the efficiency of a-Si:H solar cells. Although hydrogen is implicated in these defects, microscopic understanding of the structure and energetics of hydrogen in a-Si:H has been limited. The current limits are in part due to the lack of reliable theoretical calculations. Here we apply density functional methods to study H in a-Si:H. First, we develop a new atomistic model for a-Si:H. Then, using molecular dynamics simulations, we compare several currently available atomistic models. Finally, we calculate the properties of hydrogen in these models, including the geometric environments, the energetics, the electronic structure and the vibrational properties. Our most important conclusions are presented below. Our calculations are consistent with the following microscopic picture for long range diffusion of H in a-Si:H. Clustered Si-H bonds constitute the dominant trapping species. Upon the dissociation of 2 H atoms, a Si-Si bond forms leaving a nominally 4-fold coordinated weak bond complex. The 2 H atoms move away separately along Si-Si bond center sites until trapped at another weak bond complex. The calculated activation energy is found in agreement with established experimental results. Also, our calculations are successfully applied to observations of H evolution, hydrogen-deuterium exchange and long range diffusion in p-type amorphous silicon. Our calculations clarify the role of H during electronic defect formation. We calculate the energetics for H to move from a variety of Si-H bonds to the bulk chemical potential. For isolated Si-H bonds (i.e. in micro-cavities without any bond reconstruction) the energetics are not consistent with observations. However, if the remaining Si reconstructs with a nearby silicon creating a 5-fold coordinated defect then the energetics are in agreement with

Full Text Available We present an alternative method of depositing a high-quality passivation film for heterojunction silicon wafer solar cells, in this paper. The deposition of hydrogenated intrinsic amorphous silicon suboxide is accomplished by decomposing hydrogen, silane, and carbon dioxide in an industrial remote inductively coupled plasma platform. Through the investigation on CO2 partial pressure and process temperature, excellent surface passivation quality and optical properties are achieved. It is found that the hydrogen content in the film is much higher than what is commonly reported in intrinsic amorphous silicon due to oxygen incorporation. The observed slow depletion of hydrogen with increasing temperature greatly enhances its process window as well. The effective lifetime of symmetrically passivated samples under the optimal condition exceeds 4.7 ms on planar n-type Czochralski silicon wafers with a resistivity of 1 Ωcm, which is equivalent to an effective surface recombination velocity of less than 1.7 cms−1 and an implied open-circuit voltage (Voc of 741 mV. A comparison with several high quality passivation schemes for solar cells reveals that the developed inductively coupled plasma deposited films show excellent passivation quality. The excellent optical property and resistance to degradation make it an excellent substitute for industrial heterojunction silicon solar cell production.

The construction of a Hg-photo-CVD device is discussed. The system enables the manufacturing of hydrogenous thin films of amorphous silicon from monosilane compound. The reaction mechanisms taking place in the gaseous phase and at the surface, and the optimal conditions for the amorphous silicon film growth are studied. The analysis technique is based on the measurement of the difference between the condensation points of the gaseous components of the mixture obtained from the monosilane photolysis. A kinetic simplified model is proposed. Conductivity measurements are performed and the heat treatment effects are analyzed. Trace amounts of oxygen and carbon are found in the material. No Hg traces are detected by SIMS analysis [fr

Hydrogen bonding interactions in amorphous indomethacin and amorphous solid dispersions of indomethacin with poly(vinylpyrrolidone), or PVP, and poly(vinylpyrrolidone-co-vinyl acetate), or PVP/VA, were investigated quantitatively using solid-state NMR spectroscopy. Indomethacin that was (13)C isotopically labeled at the carboxylic acid carbon was used to selectively analyze the carbonyl region of the spectrum. Deconvolution of the carboxylic acid carbon peak revealed that 59% of amorphous indomethacin molecules were hydrogen bonded through carboxylic acid cyclic dimers, 15% were in disordered carboxylic acid chains, 19% were hydrogen bonded through carboxylic acid and amide interactions, and the remaining 7% were free of hydrogen bonds. The standard dimerization enthalpy and entropy of amorphous indomethacin were estimated to be -38 kJ/mol and -91 J/(mol · K), respectively, using polystyrene as the "solvent". Polymers such as PVP and PVP/VA disrupted indomethacin self-interactions and formed hydrogen bonds with the drug. The carboxylic acid dimers were almost completely disrupted with 50% (wt) of PVP or PVP/VA. The fraction of disordered carboxylic acid chains also decreased as the polymer content increased. The solid-state NMR results were compared with molecular dynamics (MD) simulations from the literature. The present work highlights the potential of (13)C solid-state NMR to detect and quantify various hydrogen bonded species in amorphous solid dispersions as well as to serve as an experimental validation of MD simulations.

Hydrogen as a fuel source is an attractive, relatively clean alternative to fossil fuels. However, a major limitation in its use for the application of automobiles has been the requirement for an efficient hydrogen storage medium. Current hydrogen storage systems are: physical storage in high pressure tanks, metal hydride, and gas-on-solid absorption. However, these methods do not fulfill the Department of Energy's targeted requirements for a usable hydrogen storage capacity of 6.5 wt.%, operation near ambient temperature and pressure, quick extraction and refueling, reliability and reusability.Reports showing high capacity hydrogen storage in single-walled carbon nanotubes originally prompted great excitement in the field, but further research has shown conflicting results. Results for carbon nanostructures have ranged from less than 1 wt.% to 70 wt.%. The wide range of adsorption found in previous experiments results from the difficulty in measuring hydrogen in objects just nanometers in size. Most previous experiments relied on weight analysis and residual gas analysis to determine the amount of hydrogen being adsorbed by the CNTs. These differing results encouraged us to perform our own analysis on single-walled (SWNTs), double-walled (DWNTs), and multi-walled carbon nanotubes (MWNTs), as well as carbon fiber. We chose to utilize direct measurement of hydrogen in the materials using elastic recoil detection analysis (ERDA). This work was supported by the National Science Foundation's Research Experience for Undergraduates and the University of North Texas.

Amorphouscarbon nanotubes; chemical synthesis; structures; oxidation resistance properties. 1. Introduction. Since the discovery of carbon ... novel route for the synthesis of a-CNTs using V3O7∙H2O and glucose solution as the starting .... symmetric band, although its asymmetric band at about. 3080 cm–1 is not observed, ...

This article reports the use of dip pen nanolithography (DPN) for the study of adsorption of bovine serum albumin (BSA) proteins on amorphouscarbon surfaces; tetrahedral amorphouscarbon (t-aC) and silicon doped hydrogenatedamorphouscarbon (a-C:H:Si). Contact angle study shows that the BSA proteins reduce the contact angle on both carbon materials. We also noticed that the drop volume dependence is consistent with a negative line tension, i.e. due to an attractive protein/surface interaction. The DPN technique was used to write short-spaced (100 nm) BSA line patterns on both samples. We found a line merging effect, stronger in the case of the a-C:H:Si material. We discuss possible contributions from tip blunting, scratching, cross-talk between lever torsion and bending and nano-shaving of the patterns. We conclude that the observed effect is caused in large measure by the diffusion of BSA proteins on the amorphouscarbon surfaces. This interpretation of the result is consistent with the contact angle data and AFM force curve analysis indicating larger tip/surface adhesion and spreading for the a-C:H:Si material. We conclude by discussing the advantages and limitations of DPN lithography to study biomolecular adsorption in nanoscale wetting environments.

Hydrogen trapped in a carbon cage, captured through repulsive interactions, is a novel concept in hydrogen storage. Trapping hydrogen via repulsive interactions borrows an idea from macroscale hydrogen storage (i.e. compressed gas storage tanks) and reapplies these concepts on the nanoscale in specially designed molecular containers. Under extreme conditions of pressure, hydrogen solubility in carbon materials is expected to increase and carbon is expected to restructure to minimize volume via a mixed sp2/sp3 hydrogenated state. Thermodynamics dictate that pre-formed C-H structures will rearrange with increased pressure, yet the final carbon-hydrogen interactions may be dependent upon the mechanism by which hydrogen is introduced. Gas “trapping” is meant to denote gas present in a solid in a high density, adsorbed-like state, when the external pressure is much less than that necessary to provide a comparable fluid density. Trapping thus denotes a kinetically metastable state rather than thermodynamic equilibrium. This project probed mechanochemical means to polymerize select hydrocarbons in the presence of gases, in an attempt to form localized carbon cages that trap gases via repulsive interactions. Aromatic, polyaromatic, and hydroaromatic molecules expected to undergo cyclo-addition reactions were polymerized at high (~GPa) pressures to form extended hydrogenatedamorphouscarbon networks. Notably, aromatics with a pre-existing internal free volume (such as Triptycene) appeared to retain an internal porosity upon application of pressure. However, a high photoluminescence background after polymerization precluded in situ identification of trapped gases. No spectroscopic evidence was found after depressurization that would be indicative of pockets of trapped gases in a localized high-pressure environment. Control studies suggested this measurement may be insensitive to gases at low pressure. Similarly, no spectral fingerprint was found for gas-imbued spherical

Concerns over climate change resulting from accumulation of anthropogenic carbon dioxide in the atmosphere and the uncertainty in the amount of recoverable fossil fuel reserves are driving forces for the development of renewable, carbon-neutral energy technologies. A promising clean solution is photoelectrochemical water splitting to produce hydrogen using abundant solar energy. Here we present a simple and scalable technique for the deposition of amorphous molybdenum sulphide films as hydrogen evolution catalyst onto protected copper(I) oxide films. The efficient extraction of excited electrons by the conformal catalyst film leads to photocurrents of up to -5.7mAcm-2 at 0V versus the reversible hydrogen electrode (pH 1.0) under simulated AM 1.5 solar illumination. Furthermore, the photocathode exhibits enhanced stability under acidic environments, whereas photocathodes with platinum nanoparticles as catalyst deactivate more rapidly under identical conditions. The work demonstrates the potential of earth-abundant light-harvesting material and catalysts for solar hydrogen production.

Depth profiles of various constituents and impurities of thin films were obtained simultaneously by a nuclear coincidence method. The energy spectrum of elastically scattered 12 MeV protons, measured by a high-resolution magnetic spectrometer, was used for constituent identification and total content determination. Constituents of interest were selected by software pulse height discrimination and their depth profiles were obtained from the recoil energy spectrum, measured by a surface barrier detector telescope. Thin films of Teflon, of carbon, and of amorphoushydrogenated silicon were measured. The best possible depth resolution is about 20 nm for carbon and is limited by the beam energy spread and the energy resolution of the solid state detectors.

Carbon nanotubes (CNTs) are promising candidates for use as reinforcements in next generation structural composite materials because of their extremely high specific stiffness and strength. They cannot, however, be viewed as simple replacements for carbon fibers because there are key differences between these materials in areas such as handling, processing, and matrix design. It is impossible to know for certain that CNT composites will represent a significant advance over carbon fiber composites before these various factors have been optimized, which is an extremely costly and time intensive process. This work attempts to place an upper bound on CNT composite mechanical properties by performing molecular dynamics simulations on idealized model systems with a reactive forcefield that permits modeling of both elastic deformations and fracture. Amorphouscarbon (AC) was chosen for the matrix material in this work because of its structural simplicity and physical compatibility with the CNT fillers. It is also much stiffer and stronger than typical engineering polymer matrices. Three different arrangements of CNTs in the simulation cell have been investigated: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. The SWNT and MWNT array systems are clearly idealizations, but the SWNT bundle system is a step closer to real systems in which individual tubes aggregate into large assemblies. The effect of chemical crosslinking on composite properties is modeled by adding bonds between the CNTs and AC. The balance between weakening the CNTs and improving fiber-matrix load transfer is explored by systematically varying the extent of crosslinking. It is, of course, impossible to capture the full range of deformation and fracture processes that occur in real materials with even the largest atomistic molecular dynamics simulations. With this limitation in mind, the simulation results reported here provide a plausible upper limit on

While low hole mobilities limit the current collection and efficiency of hydrogenatedamorphous silicon (a-Si:H) photovoltaic devices, attempts to improve mobility of the material directly have stagnated. Herein, we explore a method of utilizing nanostructuring of a-Si:H devices to allow for improved hole collection in thick absorber layers. This is achieved by etching an array of 150 nm diameter holes into intrinsic a-Si:H and then coating the structured material with p-type a-Si:H and a conformal zinc oxide transparent conducting layer. The inclusion of these nanoholes yields relative power conversion efficiency (PCE) increases of ∼45%, from 7.2 to 10.4% PCE for small area devices. Comparisons of optical properties, time-of-flight mobility measurements, and internal quantum efficiency spectra indicate this efficiency is indeed likely occurring from an improved collection pathway provided by the nanostructuring of the devices. Finally, we estimate that through modest optimizations of the design and fabrication, PCEs of beyond 13% should be obtainable for similar devices.

Recent reports continue to suggest high hydrogen storage capacities for some carbon nanostructures due to a stronger interaction between hydrogen and carbon. Here the interaction of hydrogen with activated charcoal, carbon nanofibers, single walled carbon nanotubes (SWNT), and electron beam ‘opened’

Carbon films synthesized by plasma-enhanced chemical vapor deposition (PECVD) and filtered cathodic vacuum arc (FCVA) exhibit a layered structure consisting of a bottom (interface) and a top (surface) layer rich in sp{sup 2} atomic carbon bonding and a middle (bulk) layer of much higher sp{sup 3} content. Because of significant differences in the composition, structure, and thickness of these layers, decreasing the film thickness may negatively affect its properties. In this study, transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to examine the effect of Ar{sup +} ion irradiation on the structure and thickness of ultrathin films of hydrogenatedamorphouscarbon (a-C:H) and hydrogen-free amorphouscarbon (a-C) deposited by PECVD and FCVA, respectively. The TEM and EELS results show that 2-min ion irradiation decreases the film thickness without markedly changing the film structure and composition, whereas 4-min ion irradiation results in significant film thinning and a moderate decrease of the sp{sup 3} content of the bulk layer. This study demonstrates that Ar{sup +} ion irradiation is an effective post-deposition process for reducing the thickness and tuning the structure of ultrathin carbon films. This capability has direct implications in the synthesis of ultrathin protective carbon overcoats for extremely high-density magnetic recording applications.

Mechanoactivation of amorphouscarbon synthesized from renewable feedstock promotes formation of multi-walled carbon nanotubes, and the best results were obtained using the feedstock of sphagnum moss. It is shown that the carbon nanotubes formed from different plant feedstock have a high sorption capacity with respect to hydrogen. (author)

Prolonging wear life of amorphouscarbon films under vacuum was an enormous challenge. In this work, we firstly reported that amorphouscarbon film as a lubricant layer containing hydrogen, oxygen, fluorine and silicon (a-C:H:O:F:Si) exhibited low friction (~0.1), ultra-low wear rate (9.0 × 10(-13) mm(3) N(-1) mm(-1)) and ultra-long wear life (>2 × 10(6) cycles) under high vacuum. We systematically examined microstructure and composition of transfer film for understanding of the underlying frictional mechanism, which suggested that the extraordinarily excellent tribological properties were attributed to the thermodynamically and structurally stable FeF2 nanocrystallites corroborated using first-principles calculations, which were induced by the tribochemical reaction.

The remote hydrogen plasma is able to create abundant S-vacancies on amorphous molybdenum sulfide (a-MoSx) as active sites for hydrogen evolution. The results demonstrate that the plasma-treated a-MoSx exhibits superior performance and higher stability than Pt in a proton exchange membrane based electrolyzers measurement as a proof-of-concept of industrial application.

Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

Graphene has attracted much attention in materials science and electronics because of its high conductivity, strong mechanical strength, excellent flexible properties, etc. The favored fabrication method of graphene is using methane by chemical vapor deposition. Through this method high quality and large-scale monolayer graphene has been prepared. However, this graphene is not suitable for use in preparation of logical transistor devices, owing to the insufficient band gap. On the other hand, graphene nanoribbon has a finite band gap and a N-doped graphene monolayer shows a low on/off current ratio. Therefore, it is necessary to develop fabrication techniques for making graphene that is appropriate for logic devices. This paper introduces an easy fabrication method that does not need a methane source, where a solid phase source transformation to crystallize graphene is carried out on polycrystalline Copper foil, and a N-doped graphene layer is produced. Bilayer graphene is found to be achieved at most hydrogen flow rates.

In this report amorphous, diamondlike, carbon and hydrocarbon films are investigated by two different methods, namely, X-ray scattering and a combination of X-ray and neutron reflectivity. As specular reflectivity probes the scattering length density profile of a sample perpendicular to its surface, the combination of X-ray and neutron reflectivity reveals the nuclei density of both carbon and hydrogen separately. This allows to calculate the concentration of hydrogen in the films, which varies in the presented experiments between 0 and 36 atomic %. This method is a new and nondestructive technique to determine the concentration of hydrogen within an error of about ±1 at. % in samples with sharp interfaces. It is well suited for thin diamondlike carbon films. X-ray scattering is used to obtain structural information on the atomic scale, especially the average carbon-carbon distance and the average coordination number of the carbon atoms. As grazing incidence diffraction experiments were not successful, free-standing films are used for the scattering experiments with synchrotron light. However, the scattered intensity for large scattering vectors is, in spite of the intense primary beam, very weak, and therefore the accuracy of the obtained structural parameter is not sufficient to prove the diamondlike properties also on the atomic scale. (au) (10 tabs., 76 ills., 102 refs.)

The properties of phosphorus doped hydrogenatedamorphous silicon carbide (a-SiCx:H) thin films, that were deposited by plasma enhanced chemical vapor deposition technique with four different carbon contents (x), were analyzed and compared with those of the intrinsic a-SiCx:H thin films. The carbon contents of the films were determined by X-ray photoelectron spectroscopy. The thickness and optical energies, such as Tauc, E04 and Urbach energies, of the thin films were determined by UV-Visible transmittance spectroscopy. The electrical properties of the films, such as conductivities and activation energies were analyzed by temperature dependent current-voltage measurements. Finally, the conduction mechanisms of the films were investigated by numerical analysis, in which the standard transport mechanism in the extended states and the nearest neighbor hopping mechanism in the band tail states were taken into consideration. It was determined that, by the effect of phosphorus doping the dominant conduction mechanism was the standard transport mechanism for all carbon contents.

Structural changes in amorphouscarbon coating the surfaces of multiwall carbon nanotubes (MWNTs) under applying an electric current were investigated by in situ transmission electron microscopy with simultaneous measurements of the bias voltage and electric current. Joule heating transformed amorphouscarbon on the surfaces of individual MWNTs suspended between gold electrodes into graphite layers even without a metal catalyst through a phase of glasslike carbon. The MWNTs after the formation of ordered surface layers sustained a high current with a density of up to 3.1 × 108 A/cm2.

This is the second volume in the NATO ASI series dealing with the topic of hydrogen in solids. The first (V. B76, Metal Hydrides) appeared five years ago and focussed primarily on crystalline phases of hydrided metallic systems. In the intervening period, the amorphous solid state has become an area of intense research activity, encompassing both metallic and non-metallic, e.g. semiconducting, systems. At the same time the problem of storage of hydrogen, which motivated the first ASI, continues to be important. In the case of metallic systems, there were early indications that metallic glasses and disordered alloys may be more corrosion resistant, less susceptible to embrittlement by hydrogen and have a higher hydrogen mobility than ordered metals or intermetallics. All of these properties are desirable for hydrogen storage. Subsequent research has shown that thermodynamic instability is a severe problem in many amorphous metal hydrides. The present ASI has provided an appropriate forum to focus on these issu...

The use of liquid hydrocarbons as energy carriers implies the use of carbon as a carrier for hydrogen to facilitate hydrogen transport and storage. The current trend for liquid energy carriers used in the transport sector is to maximize the load of hydrogen on the carbon carrier. The recently

The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces and their thicknesses increase with increasing deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies < 60 eV and increases for films grown using ion energies > 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of 4-fold to 3-fold coordinated carbon atoms.

The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces; their thicknesses increase with deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies 160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of σ- to π-bonded carbon atoms. (c) 2000 American Institute of Physics

The carbon ion energy used during filtered cathodic vacuum arc deposition determines the bonding topologies of amorphous-carbon (a-C) films. Regions of relatively low density occur near the substrate/film and film/surface interfaces; their thicknesses increase with deposition energy. The ion subplantation growth results in mass density gradients in the bulk portion of a-C in the growth direction; density decreases with distance from the substrate for films grown using ion energies <60 eV and increases for films grown using ion energies >160 eV. Films grown between these energies are the most diamondlike with relatively uniform bulk density and the highest optical transparencies. Bonding topologies evolve with increasing growth energy consistent with the propagation of subplanted carbon ions inducing a partial transformation of {sigma}- to {pi}-bonded carbon atoms. (c) 2000 American Institute of Physics.

The 1 H( 11 B, α)αα nuclear reaction is used to determine the H content and the density of amorphous semiconductor Si 1 -sub(x)Csub(x)H 2 and SiHsub(z) thin films. Rutherford backscattering is used to determine the x values and infrared transmission to study the hydrogen bonds. We have observed a transfer or/and a release of hydrogen under bombardment by various ions and we show that this last effect must be taken into account for a correct determination of the hydrogen content. An attempt is made to correlate the hydrogen release with electronic and nuclear energy losses. (orig.)

The authors show that bonded hydrogen in a-Si:H is readily exchanged by atomic deuterium when exposed to a deuterium plasma discharge. The effective diffusion coefficient for the D, H exchange, 10 -14 cm 2 /sec at 160 0 C, is comparable to that of interstitial hydrogen in c-Si

This paper reports that hydrogenatedamorphous silicon films of thickness 0.5-7 μm on molybdenum substrates were deposited from silane by dc glow discharge and studied by mass spectrometric observation of the evolution of hydrogen upon heating and correlating this information with the photoresponse. The films were found to contain two types of hydrogen, namely weak bonded hydrogen, which evolved at 365 degrees C and was the minority, and strongly bonded hydrogen, which evolved at 460-670 degrees C and was the majority. The proportion of strongly bonded hydrogen increased with increasing film thickness and with increasing substrate temperature during deposition. The total amount of hydrogen increased when the substrate temperature was decreased from 350 to 275 degrees C. The strongly bonded hydrogen resided throughout the thickness of the film, whereas the weakly bonded hydrogen resided near the film surface. The evolution of the strongly bonded hydrogen was diffusion controlled, with an activation energy of 1.6 eV. The strongly bonded hydrogen enhanced the photoresponse, whereas the weakly bonded hydrogen degraded the photoresponse

Near-infrared evanescent-wave cavity ring-down spectroscopy (CRDS) has been applied to study the defect evolution in an amorphous silicon (a-Si:H) thin film subjected to a directed beam of atomic H with a flux of (0.4–2) × 1014 cm−2 s−1. To this end, a 42 ± 2 nm a-Si:H film was grown on the total

Semiconducting amorphous partially dehydrogenated boron carbide has been explored as a neutron voltaic for operation in radiation harsh environments, such as on deep space satellites/probes. A neutron voltaic device could also be used as a solid state neutron radiation detector to provide immediate alerts for radiation workers/students, as opposed to the passive dosimetry badges utilized today. Understanding how the irradiation environment effects the electrical properties of semiconducting amorphous partially dehydrogenated boron carbide is important to predicting the stability of these devices in operation. p-n heterojunction diodes were formed from the synthesis of semiconducting amorphous partially dehydrogenated boron carbide on silicon substrates through the use of plasma enhanced chemical vapor deposition (PECVD). Many forms of structural and electrical measurements and analysis have been performed on the p-n heterojunction devices as a function of both He+ ion and neutron irradiation including: transmission electron microscopy (TEM), selected area electron diffraction (SAED), current versus voltage I(V), capacitance versus voltage C(V), conductance versus frequency G(f), and charge carrier lifetime (tau). In stark contrast to nearly all other electronic devices, the electrical performance of these p-n heterojunction diodes improved with irradiation. This is most likely the result of bond defect passivation and resolution of degraded icosahedral based carborane structures (icosahedral molecules missing a B, C, or H atom(s)).

The cold-cathode electron emission properties of amorphous tetrahedral diamondlike carbon are promising for flat-panel display and vacuum microelectronics technologies. The onset of electron emission is, typically, preceded by open-quotes conditioningclose quotes where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, we combined the spatially localized field and current of a scanning tunneling microscope tip with high-spatial-resolution characterization. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially resolved electron-energy-loss spectroscopy indicates that the predominant bonding configuration changes from predominantly fourfold to threefold coordination. copyright 1998 American Institute of Physics

Amorphous silicon films prepared from a d.c. discharge of 10% SiH 4 - 90% H 2 mixture are found to have properties similar to those made from 100% SiH 4 . These films are found to be quite stable against prolonged light exposure. The effect of nitrogen on the properties of these films was investigated. It was found that instead of behaving as a classical donor, nitrogen introduces deep levels in the material. Field effect experiments on a-Si:H films at the bottom (film-substrate interface) and the top (film-vacuum interface) of the film are also reported. (author)

Tetrahedral amorphouscarbon (ta-C) and nitrogenated tetrahedral amorphouscarbon films (ta-CN x ), deposited by double bend off plane Filtered Vacuum Cathodic Arc were annealed up to 1000 deg. C in flowing argon for 2 min. Modifications on the chemical bonding structure of the rapidly annealed films, as a function of temperature, were investigated by NEXAFS, X-ray photoelectron and Raman spectroscopies. The interpretation of these spectra is discussed. The results demonstrate that the structure of undoped ta-C films prepared at floating potential with an arc current of 80 A remains stable up to 900 deg. C, whereas that of ta-CN x containing 12 at.% nitrogen is stable up to 700 deg. C. At higher temperatures, all the spectra indicated the predominant formation of graphitic carbon. Through NEXAFS studies, we clearly observed three π* resonance peaks at the ' N K edge structure. The origin of these three peaks is not well established in the literature. However our temperature-dependant study ascertained that the first peak originates from C=N bonds and the third peak originates from the incorporation of nitrogen into the graphite like domains

Recent developments focusing on novel hydrogen storage media have helped to benchmark nanostructured carbon materials as one of the ongoing strategic research areas in science and technology. In particular, certain microporous carbon powders, carbon nanomaterials, and specifically carbon nanotubes stand to deliver unparalleled performance as the next generation of base materials for storing hydrogen. Accordingly, the main goal of this report is to overview the challenges, distinguishing trait...

Boron carbide is a technologically relevant material with importance in voltaic transduction. However, the local physical, chemical and electronic structure of low temperature deposited thin films of amorphous boron carbide is far from understood, hindering its progress in application. X-ray absorption and emission spectroscopies (XAS/XES) were applied to thin films of B4C and B5C:Hx to study the near Fermi edge structure; the films were prepared by RF magnetron sputtering and plasma enhanced chemical vapor deposition (PECVD) and were thermally treated after deposition from 400 to 800 C. XES spectra indicate a physical structure transition from amorphous to nanocrystalline at 700 C, a much lower temperature than expected from traditional physical vapor deposition or flash annealing temperatures reported. These structural differences are of significant interest to transport measurements and will be discussed as a correlation. Further, x-ray and ultraviolet photoemission were also collected as a compliment to XES/XAS and will be discussed in the context of understanding the local intra vs. intermolecular electronic structure of these boron-rich molecular based solids.

Full Text Available We investigate the ripple pattern formation on amorphouscarbon surfaces at room temperature during low energy Ne ion irradiation as a function of the ion incidence angle. Monte Carlo simulations of the curvature coefficients applied to the Bradley-Harper and Cater-Vishnyakov models, including the recent extensions by Harrison-Bradley and Hofsäss predict that pattern formation on amorphouscarbon thin films should be possible for low energy Ne ions from 250 eV up to 1500 eV. Moreover, simulations are able to explain the absence of pattern formation in certain cases. Our experimental results are compared with prediction using current linear theoretical models and applying the crater function formalism, as well as Monte Carlo simulations to calculate curvature coefficients using the SDTrimSP program. Calculations indicate that no patterns should be generated up to 45° incidence angle if the dynamic behavior of the thickness of the ion irradiated layer introduced by Hofsäss is taken into account, while pattern formation most pronounced from 50° for ion energy between 250 eV and 1500 eV, which are in good agreement with our experimental data.

In this work, we have used the grazing X-rays reflectometry technique to characterise hydrogenatedamorphous silicon thin films deposited by radio-frequency cathodic sputtering. Relfectometry measurements are taken immediately after films deposition as well as after having naturally oxidised their surfaces during a more or less prolonged stay in the ambient. For the films examined just after deposition, the role of hydrogen appears in the increase of their density. For those analysed after a short stay in the ambient, hydrogen plays a protective role against the oxidation of their surfaces. This role disappears when the stay in the ambient is so long. (author)

The incorporation of hydrogen in glow discharge a-Si:H is investigated with an isotope method. During deposition D2 or H2 is added to the silane. Although for low silane flow the incorporation of deuterium is affected by isotope exchange this process plays a minor role for high silane flow. At these

The processes described will form the H-concentration at the required depth of Si semiconductor due spin splitting of Si:H compounds with the intensive electron beams and processes of the photo stimulation of the volume diffusion. This will provide a continuous migration of hydrogen into the bulk material.

The ultrafast structural dynamics of the Si-H bond in the rigid solvent environment of an amorphous silicon thin film is investigated using two-dimensional infrared four-wave mixing techniques. The two-dimensional infrared (2DIR) vibrational correlation spectrum resolves the homogeneous line shapes ( 4ps waiting times. The Si-H stretching mode anharmonic shift is determined to be 84cm-1 and decreases slightly with vibrational frequency. The 1→2 linewidth increases with vibrational frequency. Frequency dependent vibrational population times measured by transient grating spectroscopy are also reported. The narrow homogeneous line shape, large inhomogeneous broadening, and lack of spectral diffusion reported here present the ideal backdrop for using a 2DIR probe following electronic pumping to measure the transient structural dynamics implicated in the Staebler-Wronski degradation [Appl. Phys. Lett. 31, 292 (1977)] in a-Si:H based solar cells.

In an ultra-high vacuum scanning electron microscope, the edged branches of amorphouscarbon film (∼10 nm thickness) can be continuously extended with an eye-identifying speed (on the order of ∼1 nm/s) under electron beam. Such unusual mobility of amorphouscarbon may be associated with deformation...

It is recognized that hydrogen separation membranes are a key component of the emerging hydrogen economy. A potentially exciting material for membrane separations are bulk metallic glass materials due to their low cost, high elastic toughness and resistance to hydrogen 'embrittlement' as compared to crystalline Pd-based membrane systems. However, at elevated temperatures and extended operation times structural changes including partial crystallinity may appear in these amorphous metallic systems. A systematic evaluation of the impact of partial crystallinity/devitrification on the diffusion and solubility behavior in multi-component Metallic Glass materials would provide great insight into the potential of these materials for hydrogen applications. This study will report on the development of time and temperature crystallization mapping and their use for interpretation of 'in-situ' hydrogen permeation at elevated temperatures.

This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show...

Hydrogen can be trapped in the bulk materials in four forms: interstitial molecular H2, interstitial atom H, O‑H+(2Si=O–H)+, Si‑H‑( {{4O}}\\bar \\equiv {{Si&x2212H}})‑ to affect the electronic and optical properties of amorphous silica. Therefore, the electronic and optical properties of defect-free and hydrogen defects in amorphous silica were performed within the scheme of density functional theory. Initially, the negative charged states hydrogen defects introduced new defect level between the valence band top and conduction band bottom. However, the neutral and positive charged state hydrogen defects made both the valence band and conduction band transfer to the lower energy. Subsequently, the optical properties such as absorption spectra, conductivity and loss functions were analyzed. It is indicated that the negative hydrogen defects caused the absorption peak ranging from 0 to 2.0 eV while the positive states produced absorption peaks at lower energy and two strong absorption peaks arose at 6.9 and 9.0 eV. However, the neutral hydrogen defects just improved the intensity of absorption spectrum. This may give insights into understanding the mechanism of laser-induced damage for optical materials. Project supported by the Science and Technology of Hubei Provincial Department of Education (No. B2017098).

Fabrication of hydrogenatedamorphous Germanium thin film by vacuumevaporation method and then deposition with hydrogen atom by glow dischargeplasma radio frequency has been done. This germanium amorphous (a-Ge) thinfilm involves a lot of dangling bonds in the network due to the irregularityof the atomic structures and it will decrease is conductivity. To improve theband properties of (a-Ge) thin film layer a hydrogenated plasma isintroduced. Process of introducing of the hydrogen into the a-Ge film is meanto reduce the dangling bonds so that the best electric conductivity of a Ge:Hthin film will obtained. To identify the hydrogen atom in the sample acharacterization using infrared spectrometer has been done, as well as themeasurement of conductivity of the samples. From the characterization usinginfrared spectroscopy the existence of hydrogen atom was found at absorptionpeak with wave number 1637.5 cm -1 , while the optimum conductivity of thesample 1634.86 Ω -1 cm -1 was achieved at 343 o K. (author)

Composites consisting of ruthenium oxide particles deposited on amorphouscarbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphouscarbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphouscarbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

This work demonstrates the first molecular-level conversion pathway of NO oxidation over a novel SrO-clusters@amorphouscarbon nitride (SCO-ACN) photocatalyst, which is synthesized via copyrolysis of urea and SrCO 3 . The inclusion of SrCO 3 is crucial in the formation of the amorphouscarbon nitride (ACN) and SrO clusters by attacking the intralayer hydrogen bonds at the edge sites of graphitic carbon nitride (CN). The amorphous nature of ACN can promote the transportation, migration, and transformation of charge carriers on SCO-ACN. And the SrO clusters are identified as the newly formed active centers to facilitate the activation of NO via the formation of Sr-NO δ(+) , which essentially promotes the conversion of NO to the final products. The combined effects of the amorphous structure and SrO clusters impart outstanding photocatalytic NO removal efficiency to the SCO-ACN under visible-light irradiation. To reveal the photocatalytic mechanism, the adsorption and photocatalytic oxidation of NO over CN and SCO-ACN are analyzed by in situ DRIFTS, and the intermediates and conversion pathways are elucidated and compared. This work presents a novel in situ DRIFTS-based strategy to explore the photocatalytic reaction pathway of NO oxidation, which is quite beneficial to understand the mechanism underlying the photocatalytic reaction and advance the development of photocatalytic technology for environmental remediation.

We report the finding of the presence of carbon nanoparticles (CNPs) in different carbohydrate based food caramels, viz. bread, jaggery, sugar caramel, corn flakes and biscuits, where the preparation involves heating of the starting material. The CNPs were amorphous in nature; the particles were spherical having sizes in the range of 4–30 nm, depending upon the source of extraction. The results also indicated that particles formed at higher temperature were smaller than those formed at lower temperature. Excitation tuneable photoluminescence was observed for all the samples with quantum yield (QY) 1.2, 0.55 and 0.63%, for CNPs from bread, jaggery and sugar caramels respectively. The present discovery suggests potential usefulness of CNPs for various biological applications, as the sources of extraction are regular food items, some of which have been consumed by humans for centuries, and thus they can be considered as safe. PMID:22540029

The electrical transport and resistance switching mechanism in amorphouscarbon (a-C) is investigated at the nanoscale. The electrical conduction in a-C thin films is shown to be captured well by a Poole-Frenkel transport model that involves nonisolated traps. Moreover, at high electric fields a field-induced threshold switching phenomenon is observed. The following resistance change is attributed to Joule heating and subsequent localized thermal annealing. We demonstrate that the mechanism is mostly due to clustering of the existing sp 2 sites within the sp 3 matrix. The electrical conduction behaviour, field-induced switching and Joule-heating-induced rearrangement of atomic order resulting in a resistance change are all reminiscent of conventional phase-change memory materials. This suggests the potential of a-C as a similar nonvolatile memory candidate material.

Amorphous hard carbon films of varying sp{sup 2}/sp{sup 3} fractions have been deposited on Si using filtered cathodic are deposition with pulsed biasing. The films were heat treated in air up to 550 C. Raman investigation and nanoindentation were performed to study the modification of the films caused by the heat treatment. It was found that films containing a high sp{sup 3} fraction sustain their hardness for temperatures at least up to 400 C, their structure for temperatures up to 500 C, and show a low thickness loss during heat treatment. Films containing at low sp{sup 3} fraction graphitize during the heat treatment, show changes in structure and hardness, and a considerable thickness loss.

We have measured the temperature dependence of mechanical dissipation in tetrahedral amorphouscarbon flexural and torsional resonators over the temperature range from 300 to 1023 K. The mechanical dissipation was found to be controlled by defects within the material, and the magnitude and temperature dependence of the dissipation were found to depend on whether flexural or torsional vibrational modes were excited. The defects that were active under flexural stresses have a relatively flat concentration from 0.4 to 0.7 eV with an ever increasing defect concentration up to 1.9 eV. Under shear stresses (torsion), the defect activation energies increase immediately beginning at 0.4 eV, with increasing defect concentration at higher energies.

Under consideration is the mechanism of multiwalled nanotubes formation during mechanical activation of amorphouscarbon synthesized by pyrolysis of sphagnum moss. The formation of nanotubes has been shown to take place in the array of carbon particles. A complex study of the sorption characteristics of carbon nanotubes has been carried out. The dependence of the sorption capacity of carbon nanotubes on their storage time, as well as the effect of the process parameters of nanotubes formation on their ability for oxidative modification, is represented. (authors)

Full Text Available Abstract We report graphitic carbon growth on crystalline and amorphous oxide substrates by using carbon molecular beam epitaxy. The films are characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The formations of nanocrystalline graphite are observed on silicon dioxide and glass, while mainly sp2 amorphouscarbons are formed on strontium titanate and yttria-stabilized zirconia. Interestingly, flat carbon layers with high degree of graphitization are formed even on amorphous oxides. Our results provide a progress toward direct graphene growth on oxide materials. PACS: 81.05.uf; 81.15.Hi; 78.30.Ly.

We report on fundamental discovery of conversion of amorphouscarbon into diamond by irradiating amorphouscarbon films with nanosecond lasers at room-temperature in air at atmospheric pressure. We can create diamond in the form of nanodiamond (size range <100 nm) and microdiamond (>100 nm). Nanosecond laser pulses are used to melt amorphous diamondlike carbon and create a highly undercooled state, from which various forms of diamond can be formed upon cooling. The quenching from the super undercooled state results in nucleation of nanodiamond. It is found that microdiamonds grow out of highly undercooled state of carbon, with nanodiamond acting as seed crystals

A new nanocomposite, titanium aluminum carbonitride/amorphous-carbon thin film was prepared by radio-frequency (rf) plasma-enhanced chemical-vapor deposition using titanium tetrachloride, aluminum trichloride, methane, and nitrogen as reactants. Hydrogen was used as carrier gases. A substrate temperature of 500 °C and an rf power of 100 W were used in all depositions. The films were characterized by x-ray powder diffraction, Raman spectroscopy, x-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. The results show that nanograins of titanium aluminum carbonitride were embedded in an amorphous-carbon matrix. The nanograins had a (200) preferred orientation with columnar cross-section morphology. Mechanical properties were analyzed by nanoindentation and hardness was demonstrated to increase via this microstructure design approach. The effects of microstructure on mechanical properties were also determined.

A new nanocomposite, titanium aluminum carbonitride/amorphous-carbon thin film was prepared by radio-frequency (rf) plasma-enhanced chemical-vapor deposition using titanium tetrachloride, aluminum trichloride, methane, and nitrogen as reactants. Hydrogen was used as carrier gases. A substrate temperature of 500 deg. C and an rf power of 100 W were used in all depositions. The films were characterized by x-ray powder diffraction, Raman spectroscopy, x-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. The results show that nanograins of titanium aluminum carbonitride were embedded in an amorphous-carbon matrix. The nanograins had a (200) preferred orientation with columnar cross-section morphology. Mechanical properties were analyzed by nanoindentation and hardness was demonstrated to increase via this microstructure design approach. The effects of microstructure on mechanical properties were also determined

We present an investigation on the transition from amorphous to nanocrystalline silicon and associated hydrogen changes during the first steps of hydrogenated nanocrystalline silicon growth for films elaborated by reactive radiofrequency magnetron sputtering at a substrate temperature as low as room temperature and for deposition times varying from 3 to 60 min. Complementary experimental techniques have been used to characterize the films in their as-deposited state. They are completed by thermal hydrogen effusion experiments conducted in the temperature range, from room temperature to 800 Degree-Sign C. The results show that, during the initial stages of growth, the presence of a hydrogen-rich layer is necessary to initiate the crystallization process. - Highlights: Black-Right-Pointing-Pointer Nanocrystalline silicon growth at room temperature. Black-Right-Pointing-Pointer Transition from amorphous to nanocrystalline silicon. Black-Right-Pointing-Pointer Chemical reactions of H atoms with strained Si-Si bonds. Black-Right-Pointing-Pointer H selective etching and chemical transport caused the silicon nucleation.

Genetic programming is used to identify the structural features most strongly associated with hole traps in hydrogenated nanocrystalline silicon with very low crystalline volume fraction. The genetic programming algorithm reveals that hole traps are most strongly associated with local structures within the amorphous region in which a single hydrogen atom is bound to two silicon atoms (bridge bonds), near fivefold coordinated silicon (floating bonds), or where there is a particularly dense cluster of many silicon atoms. Based on these results, we propose a mechanism by which deep hole traps associated with bridge bonds may contribute to the Staebler-Wronski effect.

An in situ method based on attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is presented for detecting surface silicon hydrides on plasma deposited hydrogenatedamorphous silicon (a-Si:H) films and for determining their surface concentrations. Surface silicon hydrides are desorbed by exposing the a-Si:H films to low energy ions from a low density Ar plasma and by comparing the infrared spectrum before and after this low energy ion bombardment, the absorptions by surface hydrides can sensitively be separated from absorptions by bulk hydrides incorporated into the film. An experimental comparison with other methods that utilize isotope exchange of the surface hydrogen with deuterium showed good agreement and the advantages and disadvantages of the different methods are discussed. Furthermore, the determination of the composition of the surface hydrogen bondings on the basis of the literature data on hydrogenated crystalline silicon surfaces is presented, and quantification of the h...

The results of measurements on co-deposition of hydrogen isotopes and wall materials, hydrogen retention, redeposition of carbon and deposition of hydrogen on PMI of JT-60U are described. From above results, selection of plasma facing material and ability of carbon wall is discussed. Selection of plasma facing materials in fusion reactor, characteristics of carbon materials as the plasma facing materials, erosion, transport and deposition of carbon impurity, deposition of tritium in JET, results of PMI in JT-60, application of carbon materials to PFM of ITER, and future problems are stated. Tritium co-deposition in ITER, erosion and transport of carbon in tokamak, distribution of tritium deposition on graphite tile used as bumper limiter of TFTR, and measurement results of deposition of tritium on the Mark-IIA divertor tile and comparison between them are described. (S.Y.)

In the present work it is studied the activated carbon of mineral origin for the sorption of hydrogen. The carbon decreased of particle size by means of the one alloyed mechanical. The time of mill was of 10 hours. The characterization one carries out by scanning electron microscopy and X-ray diffraction. The hydrogen sipped in the carbon material it was determined using the Thermal gravimetric method (TGA). The conditions of hydrogenation went at 10 atm of pressure and ambient temperature during 18 hours. They were also carried out absorption/desorption cycles of hydrogen in the same one system of thermal gravimetric analysis. The results showed percentages of sorption of 2% approximately in the cycles carried out in the system TGA and of 4.5% in weight of hydrogen at pressure of 10 atmospheres and ambient temperature during 18 hours. (Author)

An efficient, cost-effective hydrogen storage system is a key enabling technology for the widespread introduction of hydrogen fuel cells to the domestic marketplace. Air Products, an industry leader in hydrogen energy products and systems, recognized this need and responded to the DOE 'Grand Challenge' solicitation (DOE Solicitation DE-PS36-03GO93013) under Category 1 as an industry partner and steering committee member with the National Renewable Energy Laboratory (NREL) in their proposal for a center-of-excellence on Carbon-Based Hydrogen Storage Materials. This center was later renamed the Hydrogen Sorption Center of Excellence (HSCoE). Our proposal, entitled 'Designing Microporous Carbons for Hydrogen Storage Systems,' envisioned a highly synergistic 5-year program with NREL and other national laboratory and university partners.

A study of the formation of voids and molecular hydrogen in hydrogenatedamorphous silicon is presented based upon a hybrid approach that involves inversion of experimental nuclear magnetic resonance data in conjunction with ab initio total-energy relaxations in an augmented solution space. The novelty of this approach is that the voids and molecular hydrogen appear naturally in the model networks unlike conventional approaches, where voids are created artificially by removing silicon atoms from the networks. Two representative models with 16 and 18 at. % of hydrogen are studied in this work. The result shows that the microstructure of the a-Si:H network consists of several microvoids and few molecular hydrogen for concentration above 15 at. % H. The microvoids are highly irregular in shape and size, and have a linear dimension of 5–7 Å. The internal surface of a microvoid is found to be decorated with 4–9 hydrogen atoms in the form of monohydride Si–H configurations as observed in nuclear magnetic resonance experiments. The microstructure consists of (0.9–1.4)% hydrogen molecules of total hydrogen in the networks. These observations are consistent with the outcome of infrared spectroscopy, nuclear magnetic resonance, and calorimetry experiments.

We present new interferometric H I and optical observations of three amorphous galaxies, systems with a smooth, high surface brightness but an asymmetrical distribution of light. All three galaxies are forming stars and have LMC-like emission-line ratios, low dust content, and high H I velocity dispersions. NGC 1140 has a boxy inner morphology with a hook off one corner. At low light levels unusual extensions of starlight are seen curving to the northwest and southeast. The galaxy contains a very luminous central star-forming region and a small chain of H II regions that coincide with the hook. The central H II region has broad H(alpha) velocity profiles full width at half maximum (FWHM) less than or equal to 140 km/s, and it is a radio continuum source. There is a rotating H I gas disk, 40 kpc in radius, at a position angle 51 deg from the optical major axis. The central gas ridge follows the chain of H II regions, and the H I peak is on the hook. The outer gas on the southeast side curves away from the H I major axis. The central gas density is high, and the surface density declines very slowly with radius. The rotation velocity yields a mass of 1 x 10(exp 11) solar mass at 3.3 Holmberg radii (R(sub H)). NGC 1800 has a hook that coincides with a large H II region, and an r(exp 1/4) luminosity distribution. There are numerous H II regions along the major axis and extraordinary filaments of ionized gas. Emanating from the major axis on either side of the galaxy are H(alpha) fingers approximately 750 pc long. About 2.3 kpc to the north is a web of filaments approximately 3 kpc in extent. H(alpha) profiles of H II regions and filaments are narrow. The H I gas disk has a position angle that is approximately 13 deg different from that of the optical axis. There are two peaks near the center, one of which is near the largest H II region. Beyond the Holmberg radius to the west is a 6 x 10(exp 6) solar mass H I cloud. Its velocity indicates a mass of approximately 6 x 10

Recent reports continue to suggest high hydrogen storage capacities for some carbon nanostructures due to a stronger interaction between hydrogen and carbon. Here the interaction of hydrogen with activated charcoal, carbon nanofibers, single walled carbon nanotubes (SWNT), and electron beam 'opened' SWNT are compared and shown to be similar. The storage capacity below 77 K of these materials correlates with the surface area of the material with the activated charcoal having the largest. SWNT and 'opened' SWNT have a relatively low accessible surface area due to bundling of the tubes. Pressure-temperature curves give the interaction potential, which was found to be ∼580 K or 50 meV in all samples, leading to significant adsorption below ∼50 K. Using the inelastic neutron scattering signal associated with rotation of the hydrogen molecule as a sensitive probe for the surroundings of the molecule, no difference was found between the hydrogen molecules adsorbed in the investigated materials. These combined spectroscopic and macroscopic results show that SWNT, nanofibers and activated carbons store molecular hydrogen due to their graphitic nature and not because they possess special morphologies. Results from a density functional theory computer calculation suggest molecular hydrogen bonding to an aromatic C-C bond of graphite, irrespective of the surface morphology farther away

In this study we investigate carbon isotope fractionation during the crystallization of biogenic calcium carbonate. Several species of earthworm including Lumbricus terrestris secrete CaCO 3 . Initially a milky fluid comprising micro-spherules of amorphous CaCO 3 (ACC) is secreted into pouches of the earthworm calciferous gland. The micro-spherules coalesce and crystalize to form millimetre scale granules, largely comprising calcite. These are secreted into the earthworm intestine and from there into the soil. L. terrestris were cultured for 28 days in two different soils, moistened with three different mineral waters at 10, 16 and 20 °C. The milky fluid in the calciferous glands, granules in the pouches of the calciferous glands and granules excreted into the soil were collected and analysed by FTIR spectroscopy to determine the form of CaCO 3 present and by IRMS to determine δ 13 C values. The milky fluid was ACC. Granules removed from the pouches and soil were largely calcite; the granules removed from the pouches contained more residual ACC than those recovered from the soil. The δ 13 C values of milky fluid and pouch granules became significantly more negative with increasing temperature (p ≤ 0.001). For samples from each temperature treatment, δ 13 C values became significantly (p ≤ 0.001) more negative from the milky fluid to the pouch granules to the soil granules (−13.77, −14.69 and −15.00 respectively at 10 °C; −14.37, −15.07 and −15.18 respectively at 16 °C and −14.89, −15.41 and −15.65 respectively at 20 °C). Fractionation of C isotopes occurred as the ACC recrystallized to form calcite with the fractionation factor ε calcite-ACC = −1.20 ± 0.52‰. This is consistent with the crystallization involving dissolution and reprecipitation rather than a solid state rearrangement. Although C isotopic fractionation has previously been described between different species of dissolved inorganic carbon and

Amorphous Ni-based alloy membranes show great promise as inexpensive, hydrogenselective membrane materials. In this study, we developed membranes based on nonprecious Ni-Nb-Zr alloys by adjusting the alloying content and using additives. Several studies on crystallization of the amorphous ribbons, in-situ x-ray diffraction, SEM and TEM, hydrogen permeation, hydrogen solubility, hydrogen deuterium exchange, and electrochemical studies were conducted. An important part of the study was to completely eliminate Palladium coatings of the NiNbZr alloys by hydrogen heattreatment. The amorphous alloy (Ni0.6Nb0.4)80Zr20 membrane appears to be the best with high hydrogen permeability and good thermal stability.

Deposition of low secondary electron yield (SEY) carbon coatings by magnetron sputtering onto the inner walls of the accelerator seems to be the most promising solution for suppressing the electron cloud problem. However, these coatings change their electron emission properties during long term exposure to air. The ageing process of carbon coated samples with initial SEY of about 0.9 received from CERN is studied as a function of exposure to different environments. It is shown that samples having the same initial SEY may age with different rates. The SEY increase can be correlated with the surface concentration of oxygen. Annealing of samples in air at 100-200 {\\deg}C reduces the ageing rate and even recovers previously degraded samples. The result of annealing is reduction of the hydrogen content in the coatings by triggering its surface segregation followed by desorption.

The Car-Parrinello method for carrying out molecular dynamics enables the forces between atoms to be calculated by solving Schroedinger's equation for the valence electrons using Density Functional Theory. The method is capable of giving good structural predictions for amorphous network solids by quenching from the melt, even in situations where the bonding changes from one site to another. In amorphouscarbon where, depending on its environment, carbon may show sp 2 or sp 3 bonds. The method is applied here to the study of network solids using the example of tetrahedral amorphouscarbon

Charge carrier dynamics in amorphous semiconductors has been a topic of intense research that has been propelled by modern applications in thin-film solar cells, transistors and optical sensors. Charge transport in these materials differs fundamentally from that in crystalline semiconductors owing to the lack of long-range order and high defect density. Despite the existence of well-established experimental techniques such as photoconductivity time-of-flight and ultrafast optical measurements, many aspects of the dynamics of photo-excited charge carriers in amorphous semiconductors remain poorly understood. Here, we demonstrate direct imaging of carrier dynamics in space and time after photo-excitation in hydrogenatedamorphous silicon (a-Si:H) by scanning ultrafast electron microscopy (SUEM). We observe an unexpected regime of fast diffusion immediately after photoexcitation, together with spontaneous electron-hole separation and charge trapping induced by the atomic disorder. Our findings demonstrate the rich dynamics of hot carrier transport in amorphous semiconductors that can be revealed by direct imaging based on SUEM.

The search for cost effective adsorbents for large scale gas separation, storage and transport constitutes a present day strategic issue in the energy sector, propelled mainly by the potential use of hydrogen as an energy vector in a sustainable (and cleaner) energy scenario. Both, activated carbons and carbon based nano-structured materials have been proposed as potential candidates for reversible hydrogen storage in cryogenically cooled vessels. For that purpose, surface modification so as to enhance the gas solid interaction energy is desirable. We report on hydrogen adsorption on microporous (active) carbons which have been partially oxidised with nitric acid and ammonium persulfate. From the corresponding hydrogen adsorption isotherms (Fig. 1) an isosteric heat of about 3 kJ mol -1 was derived. This value is in agreement with that of about 3 to 4 kJ mol -1 obtained by quantum chemical calculations on the interaction between the hydrogen molecule and simple model systems (Fig. 2) of both, hydroxyl and carboxyl groups. Further research is in progress with a view to further increases the gas solid interaction energy. However, the values so far obtained are significantly larger than the liquefaction enthalpy of hydrogen: 0.90 kJ mol -1 ; and this is relevant to both, hydrogen separation from gas mixtures and cryogenic hydrogen storage. (authors)

Fluorinated amorphouscarbon (a-C:F) films were deposited by radio frequency bias assisted microwave plasma electron cyclotron resonance chemical vapor deposition with tetrafluoromethane (CF4) and acetylene (C2H2) as precursors. The deposition process was performed at two flow ratios R=0.90 and R=0.97, where R=CF4/(CF4+C2H2). The samples were annealed at 300 °C for 30 min. in a N2 atmosphere. Both Fourier transform infrared and electron spectroscopy for chemical analyzer were used to characterize the a-C:F film chemical bond and fluorine concentration, respectively. A high resolution electron energy loss spectrometer was applied to detect the electronic structure. The higher CF4 flow ratio (R=0.97) produced more sp3 linear structure, and it made the a-C:F film smoother and softer. A lifetime of around 0.34 μs and an energy gap of ˜2.75 eV were observed in both the as-deposited and after annealing conditions. The short carriers lifetime in the a-C:F film made the photoluminescence peak blueshift. The annealing changed both the structure and composition of the a-C:F film. The type of fluorocarbon bond and electronic structure characterized the mechanical and physical properties of a-C:F film.

The IV characteristics of pin solar cells made of amorphous, polymorphous and microcrystalline silicon were investigated. The temperature dependence was measured in the temperature range between 150 K and 395 K. This range covers the most terrestrial applications condition. Using simplex procedure, the IV parameter of the cells were deduce using line fitting. It has been shown that polymorphous silicon shows electrical properties that are close to properties of microcrystalline silicon but as it is well known, polymorphous silicon shows higher absorption similar to amorphous silicon. The polymorphous silicon solar cells showed higher efficiencies, lower shunting and higher filling factors. In the above mentioned temperature range, polymorphous silicon is the better material for the manufacturing of thin film hydrogenated silicon pin solar cells. More investigations concerning the structural properties are necessary to make stronger conclusions in regards to the stability of the material, what we hope to do in the future. (author)

Mixed-phase hydrogenated silicon oxide (SiOx:H) is applied to thin-film hydrogenatedamorphous silicon germanium (a-SiGe:H) solar cells serving as both p-doped and n-doped layers. The bandgap of p-SiOx:H is adjusted to achieve a highly-transparent window layer while also providing a strong electric

The use of liquid hydrocarbons as energy carriers implies the use of carbon as a carrier for hydrogen to facilitate hydrogen transport and storage. The current trend for liquid energy carriers used in the transport sector is to maximize the load of hydrogen on the carbon carrier. The recently developed Shell Middle Distillate Hydrogenation process for the manufacture of high quality diesel from aromatic refinery streams fits this picture. In the future, the hydrogen required to raise the product H/C ratio will be increasingly produced via gasification of large amounts of heavy residues. In the light of the strong preference towards using liquid fuels in the transport sector, the Shell Middle Distillate Synthesis process to convert natural gas into diesel of very high quality is discussed. Finally, a few comments on the use of hydrogen without a carbon carrier are made. Long lead times and the likelihood of producing the 'first' hydrogen from fossil fuel are highlighted. 13 figs., 6 tabs., 5 refs

We propose hydrogenatedamorphous silicon nanowires as a platform for nonlinear optics in the telecommunication wavelength range. Extraction of the nonlinear parameter of these photonic nanowires reveals a figure of merit larger than 2. It is observed that the nonlinear optical properties...... of these waveguides degrade with time, but that this degradation can be reversed by annealing the samples. A four wave mixing conversion efficiency of + 12 dB is demonstrated in a 320 Gbit/s serial optical waveform data sampling experiment in a 4 mm long photonic nanowire....

We report enhanced photoluminescence in the telecommunications wavelength range in ring resonators patterned in hydrogenatedamorphous silicon thin films deposited via low-temperature plasma enhanced chemical vapor deposition. The thin films exhibit broadband photoluminescence that is enhanced by up to 5 dB by the resonant modes of the ring resonators due to the Purcell effect. Ellipsometry measurements of the thin films show a refractive index comparable to crystalline silicon and an extinction coefficient on the order of 0.001 from 1300 nm to 1600 nm wavelengths. The results are promising for chip-scale integrated optical light sources.

The present work is essentially focused on the study of optical and structural properties of hydrogenatedamorphous silicon thin films (a-Si:H) prepared by radio-frequency cathodic sputtering. We examine separately the influence of hydrogen partial pressure during film deposition, and the effect of post-deposition thermal annealings on the main optical characteristics of the layers such as refraction index, optical gap and Urbach energy. Using the grazing X-rays reflectometry technique, thin film structural properties are examined immediately after films deposition as well as after surface oxidation or annealing. We show that low hydrogen pressures allow a saturation of dangling bonds in the layers, while high doses lead to the creation of new defects. We show also that thermal annealing under moderate temperatures improves the structural quality of the deposited layers. For the films examined just after deposition, the role of hydrogen appears in the increase of their density. For those analysed after a short stay in the ambient, hydrogen plays a protective role against the oxidation of their surfaces. This role disappears for a long time stay in the ambient. (author)

Hydrogenatedamorphous silicon (a-Si:H) films have been widely applied to semiconductor devices, such as thin film transistors, solar cells and photosensitive devices. In this work, the first Si-H-Cl alloys (obtained at the National Institute for Nuclear Research of Mexico) were formed by a microwave electron cyclotron resonance (Ecr) plasma CVD method. Gaseous mixtures of silicon tetrachloride (Si Cl 4 ), hydrogen and argon were used. The Ecr plasma was generated by microwaves at 2.45 GHz and a magnetic field of 670 G was applied to maintain the discharge after resonance condition (occurring at 875 G). Si and Cl contents were analyzed by Rutherford Backscattering Spectrometry (RBS). It was found that, increasing proportion of Si Cl 4 in the mixture or decreasing pressure, the silicon and chlorine percentages decrease. Optical gaps were obtained by spectrophotometry. Decreasing temperature, optical gap values increase from 1.4 to 1.5 eV. (Author)

Amorphouscarbon (a-C) has extensively been studied in the last two decades due to many superior properties. Amorphouscarbon was successfully prepared by carbonization of organic compounds exposed up to 200°C. Organic compounds that used in this research were coconut sap, lontar palm sap and their derivatives. The X-ray diffraction pattern shows that carbonization of organic compounds produce amorphouscarbon phase at 2θ =20°. The infrared absorption in the region from 500 to 4000 cm-1 were resolved into several peaks, which were assigned to C-H, C=C, C-O, C=O and O-H. Four point probe method was also used to measure the conductivity and band gap of each material, resulting in 1.73 - 29.6 S/m and 0.08 - 0.49 eV respectively.

The chemical and electronic structure, as related to the surface, interface and bulk of amorphoushydrogenated boron carbide (a-BxC:H y), is of interest in neutron detection and microelectronics. This dissertation investigates the chemical and electronic structure of semiconducting thin-film a-BxC:Hy grown by plasma enhanced chemical vapor deposition (PECVD) of ortho-carborane (1,2-C2B10H12). Experimental methods used include: x-ray and ultraviolet photoelectron spectroscopies (XPS/UPS) and x-ray absorption/emission spectroscopies (XAS/XES). These methods were used to investigate the chemical species, bonding and hybridizations, and band gaps of a-BxC:Hy prepared or treated under varying conditions. Additionally, a detailed examination of the formation of Schottky barriers was implemented. Throughout this dissertation the chemical structure was studied. One study was to understand various growth conditions. The effects of the PECVD growth parameters were evaluated by comparing changes in atomic percentages (at.%'s) between thin-films from various substrate temperatures. Additionally, detailed studies of the photoelectron core level under two different growth conditions were undertaken to evaluate the effects of pre-/post- argon ion etching (Ar+) for the following: the chemical structural change for both an as grown (AG) and in-situ thermal treatment (500°C), and post Ar+ etch of samples thermally treated ranging from as grown to 850°C. The as grown and in-situ treated samples were used in conjunction to determine the formation of the Schottky barrier. The electronic structure was determined by the changes within the valence band of the thermally treated samples and formation of Schottky barrier. Thermally treated samples (as grown to 850°C) were further evaluated with respect to their occupied and unoccupied electronic states. The atomic percentage gave a stoichiometry range for a-B xC:Hy (given as x=1.5 to 3.0 with y= decreases with thermal treatment and Oz: z

The thermal stability in vacuum of amorphous tetrahedrally coordinated carbon (a-tC) films grown on Si has been assessed by in situ Raman spectroscopy. Films were grown in vacuum on room-temperature substrates using laser fluences of 12, 22, and 45 J/cm2 and in a background gas of either hydrogen or nitrogen using a laser fluence of 45 J/cm2. The films grown in vacuum at high fluence (≳20J/cm2) show little change in the a-tC Raman spectra with temperature up to 800 °C. Above this temperature the films convert to glassy carbon (nanocrystalline graphite). Samples grown in vacuum at lower fluence or in a background gas (H2 or N2) at high fluence are not nearly as stable. For all samples, the Raman signal from the Si substrate (observed through the a-tC film) decreases in intensity with annealing temperature indicating that the transparency of the a-tC films is decreasing with temperature. These changes in transparency begin at much lower temperatures (˜200 °C) than the changes in the a-tC Raman band shape and indicate that subtle changes are occurring in the a-tC films at lower temperatures.

Research highlights: → Thin film amorphous C/Si. Good cycling response validates carbon matrix for Silicon anodes. → Thin film amorphous C/Si/C. Good cycling response validates carbon as an interface and matrix. - Abstract: The buffering effect of carbon on the structural stability of amorphous silicon films, used as an anode for lithium ion rechargeable batteries, has been studied during long term discharge/charge cycles. To this extent, the electrochemical performance of a prototype material consisting of amorphous Si thin film (∼250 nm) deposited by radio frequency magnetron sputtering on amorphouscarbon (∼50 nm) thin films, denoted as a-C/Si, has been investigated. In comparison to pure amorphous Si thin film (a-Si) which shows a rapid fade in capacity after 30 cycles, the a-C/Si exhibits excellent capacity retention displaying ∼0.03% fade in capacity up to 50 cycles and ∼0.2% after 50 cycles when cycled at a rate of 100 μA/cm 2 (∼C/2) suggesting that the presence of thin amorphous C layer deposited between the Cu substrate and a-Si acts as a buffer layer facilitating the release of the volume induced stresses exhibited by pure a-Si during the charge/discharge cycles. This structural integrity combined with microstructural stability of the a-C/Si thin film during the alloying/dealloying process with lithium has been confirmed by scanning electron microscopy (SEM) analysis. The buffering capacity of the thin amorphouscarbon layer lends credence to its use as the likely compliant matrix to curtail the volume expansion related cracking of silicon validating its choice as the matrix for bulk and thin film battery systems.

Sarin and soman are warfare nerve agents that represent some of the most toxic compounds ever synthesized. The extreme risk in handling such molecules has, until now, precluded detailed research into the surface chemistry of agents. We have developed a surface science approach to explore the fundamental nature of hydrogen bonding forces between these agents and a hydroxylated surface. Infrared spectroscopy revealed that both agents adsorb to amorphous silica through the formation of surprisingly strong hydrogen-bonding interactions with primarily isolated silanol groups (SiOH). Comparisons with previous theoretical results reveal that this bonding occurs almost exclusively through the phosphoryl oxygen (P═O) of the agent. Temperature-programmed desorption experiments determined that the activation energy for hydrogen bond rupture and desorption of sarin and soman was 50 ± 2 and 52 ± 2 kJ/mol, respectively. Together with results from previous studies involving other phosphoryl-containing molecules, we have constructed a detailed understanding of the structure-function relationship for nerve agent hydrogen bonding at the gas-surface interface.

Empirical potentials have a strong effect on the hybridization and structure of amorphouscarbon and are of great importance in molecular dynamics (MD) simulations. In this work, amorphouscarbon at densities ranging from 2.0 to 3.2 g/cm 3 was modeled by a liquid quenching method using Tersoff, 2nd REBO, and ReaxFF empirical potentials. The hybridization, structure and radial distribution function G(r) of carbon atoms were analyzed as a function of the three potentials mentioned above. The ReaxFF potential is capable to model the change of the structure of amorphouscarbon and MD results are in a good agreement with experimental results and density function theory (DFT) at low density of 2.6 g/cm 3 and below. The 2nd REBO potential can be used when amorphouscarbon has a very low density of 2.4 g/cm 3 and below. Considering the computational efficiency, the Tersoff potential is recommended to model amorphouscarbon at a high density of 2.6 g/cm 3 and above. In addition, the influence of the quenching time on the hybridization content obtained with the three potentials is discussed.

temperatures than liquefaction. Last years have brought the interest in hydrogen storage in porous carbon materials, caused by the design and accessibility of new materials, such as fullerenes, carbon nano-tubes and nano-fibers. In particular the tubular carbon structures are perspective highly adsorbing materials, for their surface adsorption (on the internal and external surface of the nano-tubes), and for the effect of capillary condensation. Data presented in Table 1 show that the amount of hydrogen adsorbed on these new materials depends of their modification and on the type of carbon precursor. In this work the concept of hydrogen storage by adsorption was analyzed. The discussion is based on measurements of hydrogen adsorption on commercial active carbon in the temperature range 77 - 298 K at pressures up to 4 MPa. The amount of gas that can be stored in an adsorption system depends on the adsorbent characteristics and the operating conditions. Adsorption method was compared with another one taking into account both technical and economical aspects. The results show that the adsorption technique could provide a viable method for hydrogen storage

higher temperatures than liquefaction [3]. Last years have brought the interest in hydrogen storage in porous carbon materials, caused by the design and accessibility of new materials, such as fullerenes, carbon nano-tubes and nano-fibers. In particular the tubular carbon structures are perspective highly adsorbing materials, for their surface adsorption (on the internal and external surface of the nano-tubes), and for the effect of capillary condensation [4]. Data presented in Table 1 show that the amount of hydrogen adsorbed on these new materials depends of their modification and on the type of carbon precursor [5]. In this work the concept of hydrogen storage by adsorption was analyzed. The discussion is based on measurements of hydrogen adsorption on commercial active carbon in the temperature range 77 - 298 K at pressures up to 4 MPa. The amount of gas that can be stored in an adsorption system depends on the adsorbent characteristics and the operating conditions. Adsorption method was compared with another one taking into account both technical and economical aspects. The results show that the adsorption technique could provide a viable method for hydrogen storage. [1]G. D. Berry, A. D. Pastemak, G. D. Rambach, J. R. Smith, N. Schock, Energy. 21, 289, 1996; [2]L. Czepirski, Przem. Chem. 70, 129, 1991 (in Polish); [3]B. Buczek, L. Czepirski, Inz. Chem. Proc., 24, 545, 2003; [4]U. Huczko, Przem. Chem. 81, 19, 2002 (in Polish); [5]U. Buenger, W. Zittel, Appl. Phys. A 72, 147, 2001. (authors)

This review summarizes our most recent findings in the structure and properties of amorphous and crystalline carbon nitride coatings, synthesized by reactive magnetron sputtering. By careful control of the plasma conditions via proper choice of process parameters such as substrate bias, target power and gas pressure, one can precisely control film structure and properties. With this approach, we were able to produce amorphouscarbon nitride films with controlled hardness and surface roughness. In particular, we can synthesize ultrathin (1 nm thick) amorphouscarbon nitride films to be sufficiently dense and uniform that they provide adequate corrosion protection for hard disk applications. We demonstrated the strong correlation between ZrN (111) texture and hardness in CN sub x /ZrN superlattice coatings. Raman spectroscopy and near-edge X-ray absorption show the predominance of sp sup 3 -bonded carbon in these superlattice coatings.

A complete solar hydrogen hybrid system has been developed to convert, store and use energy from renewable energy sources. The theoretical model has been implemented in a dynamic model-based software environment and applied to real data to simulate its functioning over a one-year period. Results are used to study system design and performance. A photovoltaic sub-system directly drives a residential load and, if a surplus of energy is available, an electrolyzer to produce hydrogen which is stored in a cluster of nitrogen-cooled tanks filled with AX-21 activated carbons. When the power converted from the sun is not sufficient to cover load needs, hydrogen is desorbed from activated carbon tanks and sent to the fuel-cell sub-system so to obtain electrical energy. A set of sub-systems (bus-bar, buck- and boost-converters, inverter, control circuits), handle the electrical power according to a Programmable Logic Control unit so that the load can be driven with adequate Quality of Service. Hydrogen storage is achieved through physisorption (weak van der Waals interactions) between carbon atoms and hydrogen molecules occurring at low temperature (77 K) in carbon porous solids at relatively low pressures. Storage modeling has been developed using a Langmuir-Freundlich 1st type isotherm and experimental data available in literature. Physisorption storage provides safer operations along with good gravimetric (10.8% at 6 MPa) and volumetric (32.5 g/l at 6 MPa) storage capacities at costs that can be comparable to, or smaller than, ordinary storage techniques (compression or liquefaction). Several test runs have been performed on residential user data-sets: the system is capable of providing grid independence and can be designed to yield a surplus production of hydrogen which can be used to recharge electric car batteries or fill tanks for non-stationary uses. (author)

We present a study on the morphological evolution of hydrogenatedamorphous silicon layers obtained by plasma enhanced chemical vapor deposition at different H dilutions in the regime close to the formation of the nanocrystalline (nc-Si) phase. The role of hydrogen in the transition from the amorphous to the crystalline phase is investigated by accurate structural and chemical characterisation, from the early stages of nucleation, where the nuclei present a size slightly larger than the critical nucleus, i.e. about 0.8 nm in radius, up to the formation of crystalline grains larger than 30 nm in radius. Hydrogen is found to have a crucial role in the transition from a-Si:H to nc-Si:H, since it forms an intermediate bond-centred Si-H-Si configuration, and when the H moves away from the bond-centred location, the strained Si-Si bonds either break or relax, undergoing local structural rearrangements closer to those of c-Si. During this phase transition a part of H bonds at grain boundaries. A correlation between the structural characteristics of the crystalline phase and the bonding mechanism of Si with H through multiple hydrides, such as Si-H{sup 2} and Si-H{sup 3} is found. Particularly the SiH{sup 3} are found to be directly correlated to the shape and the size of the nanocrystallites present in the films (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

The storage of hydrogen on carbons, with densities above 10% hydrogen weight, can be used in the sector of transport. However, only the physical-sorption of this gas (which is almost perfect and boils at 20 K under atmospheric pressure) cannot explain this performance. A study of the possible sites for one hydrogen, which can take very different forms, is presented, in order to better understand the rational development of this storage mode which could reach about ten weight %. (O.M.)

We report on new laboratory results which relate directly to the observation of strongly enhanced extended red emission (ERE) by interstellar dust in H2 photodissociation zones. The ERE has been attributed to photoluminescence by hydrogenatedamorphouscarbon (HAC). We are demonstrating that exposure to thermally dissociated atomic hydrogen will restore the photoluminescence efficiency of previously annealed HAC. Also, pure amorphouscarbon (AC), not previously photoluminescent, can be induced to photoluminesce by exposure to atomic hydrogen. This conversion of AC into HAC is greatly enhanced by the presence of UV irradiation. The presence of dense, warm atomic hydrogen and a strong UV radiation field are characteristic environmental properties of H2 dissociation zones. Our results lend strong support to the HAC photoluminescence explanation for ERE.

Cocatalyst modification of photocatalysts is an important strategy to enhance the photocatalytic performance by promoting effective separation of photoinduced electron-hole pairs and providing abundant active sites. In this study, a facile in situ photodeposition method was developed to prepare amorphous CoSx-modified TiO2 photocatalysts. It was found that amorphous CoSx nanoparticles were solidly loaded on the TiO2 surface, resulting in a greatly improved photocatalytic H2-evolution performance. When the amount of amorphous CoSx was 10 wt%, the hydrogen evolution rate of the CoSx/TiO2 reached 119.7 μmol h-1, which was almost 16.7 times that of the pure TiO2. According to the above experimental results, a reasonable mechanism of improved photocatalytic performance is proposed for the CoSx/TiO2 photocatalysts, namely, the photogenerated electrons of TiO2 can rapidly transfer to amorphous CoSx nanoparticles due to the solid contact between them, and then amorphous CoSx can provide plenty of sulfur active sites to rapidly adsorb protons from solution to produce hydrogen by the photogenerated electrons. Considering the facile synthesis method, the present cheap and highly efficient amorphous CoSx-modified TiO2 photocatalysts would have great potential for practical use in photocatalytic H2 production.

Highlights: • The biologic methanation of exclusively gases like hydrogen and carbon dioxide is feasible. • Electrical energy can be stored in the established gas grid by conversion to methane. • The quality of produced biogas is very high (c CH4 = 98 vol%). • The conversion rate is depending on H 2 -flow rate. - Abstract: A new method for the methanation of hydrogen and carbon dioxide is presented. In a novel anaerobic trickle-bed reactor, biochemical catalyzed methanation at mesophilic temperatures and ambient pressure can be realized. The conversion of gaseous substrates by immobilized hydrogenotrophic methanogens is a unique feature of this reactor type. The already patented reactor produces biogas which has a very high quality (c CH4 = 97.9 vol%). Therefore, the storage of biogas in the existing natural gas grid is possible without extensive purification. The specific methane production was measured with P = 1.17 Nm CH4 3 /(m R 3 d). It is conceivable to realize the process at sites that generate solar or wind energy and sites subject to the conditions for hydrogen electrolysis (or other methods of hydrogen production). The combination with conventional biogas plants under hydrogen addition to methane enrichment is possible as well. The process enables the coupling of various renewable energy sources

The article discusses the growth behavior of carbon nanofibers (CNFs). It mentions that CNFs can be synthesized using methods such as arc-discharge, laser ablation and chemical vapor deposition. It further states that CNFs can be grown from a physical mixing of amorphouscarbon and CGO...

The tracer diffusion of hydrogen is studied in amorphous Si3N4:H films which were produced by rf magnetron reactive sputtering. The diffusion experiments were carried out in the temperature range between 700 and 1000 °C with ion implanted deuterium isotopes. Secondary ion mass spectrometry was used for depth profile analysis. While a considerable part of the tracer is immobilized due to the interaction with the implantation damage, the other part migrates freely into the film, wherefrom diffusivities are extracted. These diffusivities coincide with those obtained from a control experiment with a gas exchange technique, demonstrating that the implantation damage has no significant influence on the determination of the correct diffusivities themselves.2H transport can be described by the concept of trap limited diffusion, where the tracer atoms are temporarily trapped by intrinsic film defects, presumably nitrogen dangling bonds. For the present case of a considerably high dissociation rate of trapped hydrogen, effective diffusivities are derived which obey an Arrhenius behaviour with a large activation energy of DgrE = 3.4 eV and a pre-exponential factor of D0 = 5 × 10-4 m2 s-1. The effect on diffusion of pre-annealing the films prior to diffusion in nitrogen and possible structural rearrangements involved, as well as of charging the films with hydrogen up to 2.6 at.%, is analysed.

Tetrahedral amorphouscarbon (ta-C) consists of a mixture of sp(3)- and sp(2)-bonded carbon ranging from 60 to 40% (sp(3)/sp(3)+sp(2)) depending on the deposition conditions. The physical, chemical, and electrochemical properties depend on the sp(2)/sp(3) bonding ratio as well as the presence of incorporated impurities, such as hydrogen or nitrogen. The ability to grow ta-C at lower temperatures (25-100 °C) on a wider variety of substrates as compared to CVD diamond is an advantage of this material. Herein, we report on the structural and electrochemical properties of nitrogen-incorporated ta-C thin films (ta-C:N). The incorporation of nitrogen into the films decreases the electrical resistivity from 613 ± 60 (0 sccm N(2)) to 1.10 ± 0.07 Ω-cm (50 sccm N(2)), presumably by increasing the sp(2)-bonded carbon content and the connectedness of these domains. Similar to boron-doped diamond, these materials are characterized by a low background voltammetric current, a wide working potential window (~ 3 V), and relatively rapid electron-transfer kinetics for aqueous redox systems, including Fe(CN)(6)(-3/-4) and Ru(NH(3))(6)(+3/+2), without conventional pretreatment. Additionally, there is weak molecular adsorption of polar molecules (methylene blue) on the ta-C surface. Overall, the properties of the ta-C and ta-C:N electrodes are such that they could be excellent new choices for electroanalytical measurements.

We report a low-energy electron irradiation method to nanocrystallize the top-surface of amorphouscarbon film in electron cyclotron resonance plasma system. The nanostructure evolution of the carbon film as a function of electron irradiation density and time was examined by transmission electron microscope (TEM) and Raman spectroscopy. The results showed that the electron irradiation gave rise to the formation of sp2 nanocrystallites in the film top-surface within 4 nm thickness. The formation of sp2 nanocrystallite was ascribed to the inelastic electron scattering in the top-surface of carbon film. The frictional property of low-energy electron irradiated film was measured by a pin-on-disk tribometer. The sp2 nanocrystallized top-surface induced a lower friction coefficient than that of the original pure amorphous film. This method enables a convenient nanocrystallization of amorphous surface.

The hydrogen absorption from the gas phase was investigated for melt-quenched Zr[sub 50]Ni[sub 50-x]Cu[sub x] (0[<=]x[<=]25) amorphous alloys by weighing, by thermoelectric power (TEP) and magnetization measurements aand by electron microscopy. A strongly nonmonotonous behaviour been observed, both as a function of the charging time and the Cu-content, for several materials characteristics and also for the nature of the hydrogen-induced phase-separation. (orig.)

Recombination processes of electrons and holes in hydrogenatedamorphous silicon (a-Si:H) are reviewed in terms of our model. The long decay component of photoluminescence (PL) and the long decay of light-induced electron spin resonance (LESR) are compared, and it is concluded that radiative centres responsible for the long decay component of PL are not LESR centres that are nonradiative centres. This is consistent with our model. The mechanism of light-induced defect creation in a-Si:H and its kinetics is summarized in terms of our model. The related defects involved in the recombination processes and the light-induced defect creation in a-Si:H are discussed. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

The degradation of a thin-film hydrogenated single-junction amorphous silicon (a-Si:H) photovoltaic (PV) module has been studied. We investigated the different modes of electrical and physical degradation of a-Si:H PV modules by employing a degradation and failure assessment procedure used in conjunction with analytical techniques, including, scanning electron microscopy (SEM) and thermogravimetry. This paper reveals that due to their thickness, thin films are very sensitive to the type of degradation observed. Moreover, this paper deals with the problems associated with the module encapsulant, poly(ethylene-co-vinylacetate) (EVA). The main objective of this study was to establish the influence of outdoor environmental conditions on the performance of a thin-film PV module comprising a-Si:H single-junction cells. (author)

We exploit the properties of surface electromagnetic waves propagating at the surface of finite one dimensional photonic crystals to improve the performance of optical biosensors with respect to the standard surface plasmon resonance approach. We demonstrate that the hydrogenatedamorphous silicon nitride technology is a versatile platform for fabricating one dimensional photonic crystals with any desirable design and operating in a wide wavelength range, from the visible to the near infrared. We prepared sensors based on photonic crystals sustaining either guided modes or surface electromagnetic waves, also known as Bloch surface waves. We carried out for the first time a direct experimental comparison of their sensitivity and figure of merit with surface plasmon polaritons on metal layers, by making use of a commercial surface plasmon resonance instrument that was slightly adapted for the experiments. Our measurements demonstrate that the Bloch surface waves on silicon nitride photonic crystals outperform surface plasmon polaritons by a factor 1.3 in terms of figure of merit.

Acoustically induced second harmonic generation (AISHG) in hydrogenatedamorphous silicon (a-Si : H) films of different morphology has been observed. We have found that with increasing acoustical power, the optical SHG of Gd : YAB laser light (lambda = 2.03 mu m) increases and reaches its maximum value at an acoustical power density of about 2.10 W cm sup - sup 2. With decreasing temperature, the AISHG signal strongly increases below 48 K and correlates well with the temperature behaviour of differential scanning calorimetry indicating near-surface temperature phase transition. The AISHG maxima were observed at acoustical frequencies of 10-11, 14-16, 20-22 and 23-26 kHz. The independently performed measurements of the acoustically induced IR spectra have shown that the origin of the observed phenomenon is the acoustically induced electron-phonon anharmonicity in samples of different morphology.

A new concept of a monolithic pixel radiation detector is presented. It is based on the deposition of a film of hydrogenatedamorphous silicon (a-Si:H) on an Application Specific Integrated Circuit (ASIC) . For almost 20 years, several research groups tried to demonstrate that a-Si:H material could be used to build radiation detectors for particle physics applications. A novel approach is made by the deposition of a-Si:H directly on the readout ASIC. This technique is similar to the concept of monolithic pixel detectors, but offers considerable advantages. We present first results from tests of a n- i-p a-Si:H diode array deposited on a glass substrate and on the a- Si:H above ASIC prototype detector.

Full Text Available The mechanical strength and mixed mode I/II fracture toughness of hydrogen-free tetrahedral amorphous diamond-like carbon (ta-C films, grown by pulsed laser deposition, are discussed in connection to material flaws and its microstructure. The failure properties of ta-C were obtained from films with thicknesses 0.5–3 μm and specimen widths 10–20 μm. The smallest test samples with 10 μm gage section averaged a strength of 7.3 ± 1.2 GPa, while the strength of 20-μm specimens with thicknesses 0.5–3 μm varied between 2.2–5.7 GPa. The scaling of the mechanical strength with specimen thickness and dimensions was owed to deposition-induced surface flaws, and, only in the smallest specimens, RIE patterning generated specimen sidewall flaws. The mode I fracture toughness of ta-C films is KIc=4.4±0.4 MPam, while the results from mixed mode I/II fracture experiments with cracks arbitrarily oriented in the plane of the film compared very well with theoretical predictions.

Full Text Available Carbon nanostructures were obtained by acetylene injection into an argon plasma jet in the presence of hydrogen. The samples were synthesized in similar conditions, except that the substrate deposition temperatures TD were varied, ranging from 473 to 973 K. A strong dependence of morphology, structure, and graphitization upon TD was found. We obtained vertical aligned carbon nanotubes (VA-CNTs at low temperatures as 473 K, amorphouscarbon nanoparticles (CNPs at temperatures from about 573 to 673 K, and carbon nanowalls (CNWs at high temperatures from 773 to 973 K. Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, elastic recoil detection analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy were used to substantiate the differences in these material types. It is known that hydrogen concentration modifies strongly the properties of the materials. Different concentrations of hydrogen-bonded carbon could be identified in amorphous CNP, VA-CNT, and CNW. Also, the H : C ratios along depth were determined for the obtained materials.

By molecular dynamics simulation, the chemical vapor deposition of amorphouscarbon onto graphite and diamond surfaces was studied. In particular, we investigated the effect of source H/C ratio, which is the ratio of the number of hydrogen atoms to the number of carbon atoms in a source gas, on the deposition process. In the present simulation, the following two source gas conditions were tested: one was that the source gas was injected as isolated carbon and hydrogen atoms, and the other was that the source gas was injected as hydrocarbon molecules. Under the former condition, we found that as the source H/C ratio increases, the deposition rate of carbon atoms decreases exponentially. This exponential decrease in the deposition rate with increasing source H/C ratio agrees with experimental data. However, under the latter molecular source condition, the deposition rate did not decrease exponentially because of a chemical reaction peculiar to the type of hydrocarbon in the source gas. (author)

We report H 2 storage capacities up to 2.7 wt% at 77 K in spherical nanoporous carbons exhibiting periodic arrays of pores and surface areas between 946 and 1646 m 2/g. The materials were produced via the pyrolysis of sucrose (C 12H 22O 11) embedded inside a spherical form of MCM-48 at 1000 °C in an inert atmosphere. Our results open up new possibilities for producing carbon nanomaterials with large surface areas, which are able to store hydrogen with attractive yields.

This paper deals with amorphous carbonaceous films deposited by different ion/or plasma assisted methods (cathodic arc evaporation, ion plating, and magnetron sputtering), which show remarkable differences in density, composition and energetic state of the particle fluxes arriving at the substrate surface. The structure of the layers was characterized by electron energy loss spectroscopy, high energy electron diffraction, Raman spectroscopy, and electron microscopy. Moreover, the hardness and mass density of the layers were measured. The three deposition methods are compared with regard to their growth conditions yielding a specific layer structure. (orig.).

Greenhouse gas (carbon) emission reduction related to the beneficial use of hydrogen is an important aspect in the development and public acceptance of a greater role for hydrogen in the economy. This presentation is an overview of potential effects of the evolving regulatory framework for carbon emissions management in Canada on hydrogen infrastructure development and compare it with activities in other jurisdictions

Highlights: • The interfaces of amorphouscarbons will be graphited and antiferromagnetic. • The ferromagnetism on the Co interfaces is induced by the medium electrons. • The spin-wave excitation will change between the acoustic and optical modes. • The charge exchange in the interfaces changes the magnetism of the interfaces. - Abstract: Based on the experimental finding of the exchange bias in amorphouscarbon samples with embedded Co nanoparticles and on the graphited character of the amorphouscarbon interface confirmed by molecular dynamics simulations we have proposed the interface of graphited carbon to be antiferromagnetic. A theoretical model, which comprises the Kondo interactions in the interfaces of Co nanoparticles and the induced antiferromagnetic interactions in the graphited carbons, is employed to evaluate the ferromagnetism of the interfaces of Co nanoparticles. We have shown that the ferromagnetism of interfaces of Co nanoparticles will be enhanced by the increase of antiferromagnetic interaction as well as the increase of electron density in the graphited carbons. In particular, we found that the antiferromagnetic interactions in graphited carbons will change the spin-wave excitation in interfaces of Co nanoparticles from the quasiacoustic mode to the quasioptical one.

Because of its high electrical resistivity, low dielectric constant (κ), high thermal neutron capture cross section, and robust chemical, thermal, and mechanical properties, amorphoushydrogenated boron carbide (a-B x C:H y ) has garnered interest as a material for low-κ dielectric and solid-state neutron detection applications. Herein, we investigate the relationships between chemical structure (atomic concentration B, C, H, and O), physical/mechanical properties (density, porosity, hardness, and Young's modulus), electronic structure [band gap, Urbach energy (E U ), and Tauc parameter (B 1/2 )], optical/dielectric properties (frequency-dependent dielectric constant), and electrical transport properties (resistivity and leakage current) through the analysis of a large series of a-B x C:H y thin films grown by plasma-enhanced chemical vapor deposition from ortho-carborane. The resulting films exhibit a wide range of properties including H concentration from 10% to 45%, density from 0.9 to 2.3 g/cm 3 , Young's modulus from 10 to 340 GPa, band gap from 1.7 to 3.8 eV, Urbach energy from 0.1 to 0.7 eV, dielectric constant from 3.1 to 7.6, and electrical resistivity from 10 10 to 10 15 Ω cm. Hydrogen concentration is found to correlate directly with thin-film density, and both are used to map and explain the other material properties. Hardness and Young's modulus exhibit a direct power law relationship with density above ∼1.3 g/cm 3 (or below ∼35% H), below which they plateau, providing evidence for a rigidity percolation threshold. An increase in band gap and decrease in dielectric constant with increasing H concentration are explained by a decrease in network connectivity as well as mass/electron density. An increase in disorder, as measured by the parameters E U and B 1/2 , with increasing H concentration is explained by the release of strain in the network and associated decrease in structural disorder. All of these correlations in a

Understanding the role of citrate in the crystallization kinetics of amorphous calcium carbonate (ACC) is essential to explain the formation mechanisms, stabilities, surface properties, and morphologies of CaCO3 biominerals. It also contributes to deeper insight into fluid-mineral inte...

Deposition was done using a pulsed filtered cathodic arc with a graphite cathode. The carbon plasma is fully ionised and condenses on the substrate, forming diamond-like material but with amorphous structure. Optical properties of amorphouscarbon films on fused-silica glass were investigated and the curves of optical density have a characteristic band at approximately 950 nm. Changes of the colourimetric quantities were evaluated and compared to uncoated fused silica glass. These changes were investigated as a function of the applied substrate bias voltage using the CIE and CIELAB colour systems. It is suggested that the mechanism of absorption is related to an allowed direct transition at the amorphouscarbon films on fused silica glass. The optical energy gap of the amorphouscarbon film depends on the bias voltage applied to the substrate holder. The optical colour parameters and optical band gap indicated that there is a relation between the dominant wavelength of the reflectance in the visible range and the wavelength of the optical band gap

Graphical abstract: Low-energy electron irradiation was proposed to nanocrystallize the top-surface of the as-deposited amorphouscarbon film, and sp{sup 2} nanocrystallites formed in the film top-surface within 4 nm thickness. Display Omitted - Abstract: We report a low-energy electron irradiation method to nanocrystallize the top-surface of amorphouscarbon film in electron cyclotron resonance plasma system. The nanostructure evolution of the carbon film as a function of electron irradiation density and time was examined by transmission electron microscope (TEM) and Raman spectroscopy. The results showed that the electron irradiation gave rise to the formation of sp{sup 2} nanocrystallites in the film top-surface within 4 nm thickness. The formation of sp{sup 2} nanocrystallite was ascribed to the inelastic electron scattering in the top-surface of carbon film. The frictional property of low-energy electron irradiated film was measured by a pin-on-disk tribometer. The sp{sup 2} nanocrystallized top-surface induced a lower friction coefficient than that of the original pure amorphous film. This method enables a convenient nanocrystallization of amorphous surface.

Argon clusters formed on an amorphouscarbon substrate as deposited from the vapor phase were studied by means of transmission high energy electron diffraction using the liquid helium cryostat. Electron diffractograms were analysed on the basis of assumption that there exist a cluster size

We present results of damage studies performed at the Free-Electron LASer in Hamburg (FLASH) on amorphouscarbon (a-C). The experiment was performed in the total external reflection geometry representing the working configuration of X-ray mirrors. The 177 eV photon laser beam was focused on a 40 nm

Photobiological hydrogen production is an alternative to thermochemical and electrolytic technologies with the advantage of carbon dioxide sequestration. However, it suffers from low solar to hydrogen energy conversion efficiency due to limited light transfer, mass transfer, and nutrient medium composition. The present study aims at addressing these limitations and can be divided in three parts: (1) experimental measurements of the radiation characteristics of hydrogen producing and carbon dioxide consuming microorganisms, (2) solar radiation transfer modeling and simulation in photobioreactors, and (3) parametric experiments of photobiological hydrogen production and carbon dioxide sequestration. First, solar radiation transfer in photobioreactors containing microorganisms and bubbles was modeled using the radiative transport equation (RTE) and solved using the modified method of characteristics. The study concluded that Beer-Lambert's law gives inaccurate results and anisotropic scattering must be accounted for to predict the local irradiance inside a photobioreactor. The need for accurate measurement of the complete set of radiation characteristics of microorganisms was established. Then, experimental setup and analysis methods for measuring the complete set of radiation characteristics of microorganisms have been developed and successfully validated experimentally. A database of the radiation characteristics of representative microorganisms have been created including the cyanobacteria Anabaena variabilis, the purple non-sulfur bacteria Rhodobacter sphaeroides and the green algae Chlamydomonas reinhardtii along with its three genetically engineered strains. This enabled, for the first time, quantitative assessment of the effect of genetic engineering on the radiation characteristics of microorganisms. In addition, a parametric experimental study has been performed to model the growth, CO2 consumption, and H 2 production of Anabaena variabilis as functions of

A simple thermal chemical vapor deposition technique is employed for the pyrolysis of a natural precursor 'camphor' and deposition of carbon films on alumina substrate at higher temperatures (600-900 deg. C). X-ray diffraction measurement reveals the amorphous structure of these films. The carbon films properties are found to significantly vary with the deposition temperatures. At higher deposition temperature, films have shown predominately sp{sup 2}-bonded carbon and therefore, higher conductivity and lower optical band gap (Tauc gap). These amorphouscarbon (a-C) films are also characterized with Raman and X-ray photoelectron spectroscopy. In addition, electrical and optical properties are measured. The thermoelectric measurement shows these as-grown a-C films are p-type in nature.

Carbon micro coils (CMC) have been prepared by the catalytic pyrolysis of acetylene at 750-800 C. The as grown coils have an almost amorphous structure and contain about 1 mass% hydrogen. They have 0.1 - 10 mm coil length, 1-5 μm coil diameter, 0.1-0.5 μm coil pitch and about 100 m 2 /g specific surface area. They were graphitized, as maintaining the morphology of the coils, by heat-treating at a higher temperature than 2500 C in Ar atmosphere. The layer space (d) of graphitized CMC was determined to be 0.341 nm, forming a 'herringbone' structure with an inclination of 10-40 degree versus the coiled fiber axis, having a specific surface area of about 8 m 2 /g. The hydrogen absorption behaviors of CMC were investigated from RT to 1200 C by a thermal desorption spectrometry (TDS) using a quadrupole mass analyzer. In TDS measurements, pre-existing hydrogen, which was due to the residual acetylene incorporated into CMC on its growing, desorbed from 700 C and peaked at about 900 C. The increment in the main peak of desorbed hydrogen in the as-grown CMC heat-treated at 500 C for 1 h under high pressure of hydrogen gas (1.9 or 8.9 MPa) was not remarkable as is shown in Fig.1. While, in the CMC samples milled mechanically for 1 h at RT using a planetary ball mill, the increase of desorbed hydrogen became to be great with the hydrogen pressure (up to 8.9 MPa) on heat-treating at 500 C, as is shown in Fig.2. In these CMC samples, the building up temperature of the hydrogen desorption was shifted to a lower one and the temperature range of desorption became to be wider than those in the as-grown CMC because of the appearance of another desorption peak at about 600 C in addition to the peak ranging from 850 C to 900 C. The same kind of peak was also slightly observed in as-grown CMC (Fig.1). It is clear that this desorption at about 600 C has contributed to the remarkable increase of desorbed hydrogen in the milled CMC. In this work, values of more than 2 mass% were obtained

We demonstrate that the key step for the reaction of CO 2 with hydrogen on Ni(110) is a change of the activated molecule coordination to the metal surface. At 90 K, CO 2 is negatively charged and chemically bonded via the carbon atom. When the temperature is increased and H approaches, the H-CO 2 complex flips and binds to the surface through the two oxygen atoms, while H binds to the carbon atom, thus yielding formate. We provide the atomic-level description of this process by means of conventional ultrahigh vacuum surface science techniques combined with density functional theory calculations and corroborated by high pressure reactivity tests. Knowledge about the details of the mechanisms involved in this reaction can yield a deeper comprehension of heterogeneous catalytic organic synthesis processes involving carbon dioxide as a reactant. We show why on Ni the CO 2 hydrogenation barrier is remarkably smaller than that on the common Cu metal-based catalyst. Our results provide a possible interpretation of the observed high catalytic activity of NiCu alloys.

The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphouscarbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT

We report a simple approach to fabricate hybrid solar cells (HSCs) based on a single-walled carbon nanotube (SWCNT) film and thin film hydrogenatedamorphous silicon (a-Si:H). Randomly oriented high-quality SWCNTs with conductivity enhanced by means of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate are used as a window layer and a front electrode. A series of HSCs are fabricated in ambient conditions with varying SWCNT film thicknesses. The polymethylmethacrylate layer drop-casted on fabricated HSCs reduces the reflection fourfold and enhances the short-circuit J sc , open-circuit V oc , and efficiency by nearly 10%. A state-of-the-art J-V performance is shown for SWCNT/a-Si HSC with an open-circuit voltage of 900 mV and an efficiency of 3.4% under simulated one-sun AM 1.5 G direct illumination.

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

The surface of a screen-printed carbon electrode (SPCE) was modified by using amorphouscarbon nitride (a-CN {sub x}) thin film deposited by reactive magnetron sputtering. Scanning electron microscopy and photoelectron spectroscopy measurements were used to characterise respectively the morphology and the chemical structure of the a-CN {sub x} modified electrodes. The incorporation of nitrogen in the amorphouscarbon network was demonstrated by X ray photoelectron spectroscopy. The a-CN {sub x} layers were deposited on both carbon screen-printed electrode (SPCE) and silicon (Si) substrates. A comparative study showed that the nature of substrate, i.e. SPCE and Si, has a significant effect on both the surface morphology of deposited a-CN {sub x} film and their electrochemical properties. The improvement of the electrochemical reactivity of SPCE after a-CN {sub x} film deposition was highlighted both by comparing the shapes of voltammograms and calculating the apparent heterogeneous electron transfer rate constant.

The evaluation of the feasibility of ex situ carbonation in landfills utilizing raw natural substances (namely serpentinites as Mg-source and the CO 2 -rich fraction of biogas as C-source) was tested through a laboratory procedure comprising three steps. The first step is the acid attack of a serpentinite at 70 °C, by means of HCl 2 M, to get MgCl 2 -rich solutions. Attacks of different durations were performed to evaluate the time needed. The second step is the neutralization of the MgCl 2 -rich solution by addition of concentrated ammonia. The third (carbonation) step is mixing of the neutralized MgCl 2 -rich solution with a solution of ammonium carbonate. This was produced in a landfill by absorption of CO 2 contained in biogas in a solution of ammonia. The neutralization of acid MgCl 2 -rich solutions caused the precipitation of ferrihydrite with secondary ammonium carnallite and salammoniac, whereas abundant precipitation of Amorphous Hydrated Impure Magnesium Carbonate (AHIMC), sometimes with minor nesquehonite, occurred in the third step. This solid carbonate acts as a stable CO 2 sink up to 380 °C. The geochemical behavior of some minor elements was also investigated during the experimental processes revealing that Al, Cr and Ni were removed during neutralization (second step), in contrast to Ca which remained in the circumneutral MgCl 2 -rich solution and entered into the structure of AHIMC. During the carbonation step, precipitation of artinite, hydromagnesite, lansfordite, magnesite and nesquehonite was thermodynamically impossible as the aqueous phase was undersaturated with respect to these solid phases upon separation of AHIMC. The CO 2 sequestered through this multi-step procedure is 0.34 ton for 1 ton of serpentinite utilized. However, despite that the use of Mg-rich silicates is a suitable approach to ex situ carbonation, due to their huge availability worldwide, the CO 2 produced in making the chemicals and the overall energy balance of the

The great versatility of polymers has promoted their application in a series of ordinary situations. The development of specific devices from polymers, however, requires modifications to fit specific stipulations. In this work the surface properties of thin films grown onto polyvinylchloride (PVC) were investigated. Hydrogenatedamorphouscarbon films were deposited onto commercial PVC plates from acetylene and argon plasmas excited by radiofrequency (13.56 MHz, 70 W) power. The proportion of acetylene in the gas feed was varied against that of argon, keeping the total pressure constant at 2.5 Pa. Deposition time was 1800 s. Film elemental composition was analyzed by X-ray photoelectron spectroscopy, XPS. Water contact angle measurements were performed using the sessile drop technique. The root mean squared roughness was derived from 50 x 50 μm 2 surface topographic images, acquired by scanning probe microscopy. Nanoindentation and pin-on-disk techniques were employed on the determination of film hardness and sliding wear, respectively. Oxidation resistance was obtained through the etching rate of the samples in oxygen radiofrequency (1.3 Pa, 50 W) plasmas. From XPS analysis it was detected oxygen and nitrogen contamination in all the samples. It was also found that sp 3 /sp 2 ratio depends on the proportion of argon in the plasma. At lower argon concentrations, hardness, wear and oxidation resistances were all improved with respect to the uncoated PVC. In such conditions, the surface wettability is low indicating a moderate receptivity to water. This combination of properties, ascribed to a balance between the ion bombardment and deposition processes, is suitable for materials exposed to rigorous weathering conditions.

The dc-current stress behavior of Mo/a-SiN x H y /Mo thin-film diodes is discussed for several a-SiN x H y -plasma-deposition conditions. Current transport is governed by thermionic field emission of electrons over a reverse biased Schottky barrier. The barrier height is determined by the a-SiN x H y -plasma-deposition conditions. Therefore these back-to-back Schottky devices provide an elegant way to perform dc-current stressing at several well defined carrier densities for similar stress fields. It is shown that such experiments allow assessment of defect-state creation/anneal mechanisms in a-SiN x H y . An electron-trapping-triggered anneal mechanism accounts for the observed dependence of the defect density at the electrode injecting contact (cathode) on the hole-barrier height at the anode. Also a new microscopically detailed anneal reaction scheme is proposed. The defect-state creation/anneal mechanism is expected to be generally applicable for all silicon-rich hydrogenatedamorphous silicon alloys. copyright 1997 American Institute of Physics

It is advantageous to construct a dielectric metasurface in silicon due to its compatibility with cost-effective, mature processes for complementary metal-oxide-semiconductor devices. However, high-quality crystalline-silicon films are difficult to grow on foreign substrates. In this work, we propose and realize highly efficient structural color filters based on a dielectric metasurface exploiting hydrogenatedamorphous silicon (a-Si:H), known to be lossy in the visible regime. The metasurface is comprised of an array of a-Si:H nanodisks embedded in a polymer, providing a homogeneously planarized surface that is crucial for practical applications. The a-Si:H nanodisk element is deemed to individually support an electric dipole (ED) and magnetic dipole (MD) resonance via Mie scattering, thereby leading to wavelength-dependent filtering characteristics. The ED and MD can be precisely identified by observing the resonant field profiles with the assistance of finite-difference time-domain simulations. The completed color filters provide a high transmission of around 90% in the off-resonance band longer than their resonant wavelengths, exhibiting vivid subtractive colors. A wide range of colors can be facilitated by tuning the resonance by adjusting the structural parameters like the period and diameter of the a-Si:H nanodisk. The proposed devices will be actively utilized to implement color displays, imaging devices, and photorealistic color printing.

The electrical properties and the degradation behavior of hydrogenatedamorphous silicon alloys (a-Si1- x A x : H, with A=C, Ge, B, P) in designs of pin, pip, nin, and MOS structures are investigated by measuring the dark and light I(V) characteristics and the spectral response as well as the space-charge-limited current (SCLC), the time of flight (TOF) of carriers and the field effect (FE). These investigations give an overview of our recent work combined with new results emphasizing the physics of the a-Si:H pin solar cells. We discuss the stabilizing influence on the degradation behavior achieved by profiling the i layers of the pin solar cells with P and B. Two kinds of pin solar cells, namely glass/SnO2/p(C)in/metal and glass/metal/pin/ITO, are investigated and an explanation of their different spectral response behavior is given. SCLC measurements lead to the conclusion that trapping is also involved in the degradation mechanism, as is recombination. TOF experiments on a-Si1- x Ge x : H pin diodes indicate that the incorporation of Ge widens the tail-state distribution below the conduction band. FE measurements showed densities of gap states of about 5×l016cm-3eV-1.

AFORS-HET (automat for simulation of heterostructures) simulation was utilized to explore the physical criteria for the passivation layer in hydrogenatedamorphous/crystalline silicon heterojunction (SHJ) solar cells, by systematically investigating the solar cell current density-voltage (J-V) performance as a function of the interface defect density (D it) at the passivation layer/c-Si hetero-interface, the thickness (t) of the passivation layer, the bandgap (E g) of the passivation layer, and the density of dangling bond states (D db)/band tail states (D bt) in the band gap of the passivation layer. The corresponding impact regulations were presented clearly. Except for D it, the impacts of D db, D bt and E g are strongly dependent on the passivation layer thickness t. While t is smaller than 4-5 nm, the solar cell performance is less sensitive to the variation of D db, D bt and E g. Low D it at the a-Si:H/c-Si interface and small thickness t are the critical criteria for the passivation layer in such a case. However, if t has to be relatively larger, the microstructure, i.e. the material quality, including D db, D bt and E g, of the passivation layer should be controlled carefully. The mechanisms involved were analyzed and some applicable methods to prepare the passivation layer were proposed.

A high pressure hydrogen confinement apparatus according to one embodiment includes carbon nanotubes capped at one or both ends thereof with a hydrogen-permeable membrane to enable the high pressure confinement of hydrogen and release of the hydrogen therethrough. A hydrogen confinement apparatus according to another embodiment includes an array of multi-walled carbon nanotubes each having first and second ends, the second ends being capped with palladium (Pd) to enable the high pressure confinement of hydrogen and release of the hydrogen therethrough as a function of palladium temperature, wherein the array of carbon nanotubes is capable of storing hydrogen gas at a pressure of at least 1 GPa for greater than 24 hours. Additional apparatuses and methods are also presented.

Carbon dioxide (CO 2 ), a key greenhouse gas produced from both anthropogenic and natural sources, has been recently considered to be an important C1 building-block for the synthesis of many industrial fuels and chemicals. Catalytic hydrogenation of CO 2 using a homogeneous system is regarded as an efficient process for CO 2 valorization. This approach leads to the direct products including formic acid (HCOOH), carbon monoxide (CO), methanol (MeOH), and methane (CH 4 ). The hydrogenation of CO 2 to CO followed by alkene carbonylation provides value-added compounds, which also avoids the tedious separation and transportation of toxic CO. Moreover, the reduction of CO 2 with H 2 in the presence of amines is of significance to attain fine chemicals through catalytic formylation and methylation reactions. The synthesis of higher alcohols and dialkoxymethane from CO 2 and H 2 has been demonstrated recently, which opens access to new molecular structures using CO 2 as an important C1 source.

Room temperature photoluminescence (PL) spectrum of hydrogenatedamorphous silicon carbide (a-SiC x :H) thin films was modeled by a joint density of tail states approach. In the frame of these analyses, the density of tail states was defined in terms of empirical Gaussian functions for conduction and valance bands. The PL spectrum was represented in terms of an integral of joint density of states functions and Fermi distribution function. The analyses were performed for various values of energy band gap, Fermi energy and disorder parameter, which is a parameter that represents the width of the energy band tails. Finally, the model was applied to the measured room temperature PL spectra of a-SiC x :H thin films deposited by plasma enhanced chemical vapor deposition system, with various carbon contents, which were determined by X-ray photoelectron spectroscopy measurements. The energy band gap and disorder parameters of the conduction and valance band tails were determined and compared with the optical energies and Urbach energies, obtained by UV–Visible transmittance measurements. As a result of the analyses, it was observed that the proposed model sufficiently represents the room temperature PL spectra of a-SiC x :H thin films. - Highlights: ► Photoluminescence spectra (PL) of the films were modeled. ► In the model, joint density of tail states and Fermi distribution function are used. ► Various values of energy band gap, Fermi energy and disorder parameter are applied. ► The model was applied to the measured PL of the films. ► The proposed model represented the room temperature PL spectrum of the films.

Spectroscopic Ellipsometry was used to determine the optical and structural properties of amorphouscarbon:gold nanocomposite thin films deposited by dc magnetron co-sputtering at different deposition power. The incorporation of gold as small particles distributed in the amorphouscarbon matrix was confirmed by X-ray Diffraction, Rutherford Backscattering measurements and High Resolution Transmission Electron Microscopy. Based on these results, an optical model for the films was developed using the Maxwell-Garnett effective medium with the Drude-Lorentz model representing the optical response of gold and the Tauc-Lorentz model for the amorphouscarbon. The gold volume fraction and particle size obtained from the fitting processes were comparable to those from the physical characterization. The analysis of the ellipsometric spectra for all the samples showed strong changes in the optical properties of the carbon films as a consequence of the gold incorporation. These changes were correlated to the structural modification observed by Raman Spectroscopy, which indicated a clustering of the sp{sup 2} phase with a subsequent decrease in the optical gap. Finally, measurements of Reflection and Transmission Spectroscopy were carried out and Transmission Electron Microscopy images were obtained in order to support the ellipsometric model results.

To understand the mechanical properties of amorphouscarbon (a-C)/boron nitride nanotube (BNNT) nanostructures, in situ mechanical tests are conducted inside a transmission electron microscope equipped with an integrated atomic force microscope system. The nanotube structure is modified with amorphouscarbon deposited by controlled electron beam irradiation. We demonstrate multiple in situ tensile, compressive, and lap shear tests with a-C/BNNT hybrid nanostructures. The tensile strength of the a-C/BNNT hybrid nanostructure is 5.29 GPa with about 90 vol% of a-C. The tensile strength and strain of the end-to-end joint structure with a-C welding is 0.8 GPa and 5.2% whereas the lap shear strength of the side-by-side joint structure with a-C is 0.25 GPa.

Highlights: • Hydrogenation of the surfaces had the effect of reducing the roughness by way of shadow etching. • Roughness was the driving factor affecting the wettability of the hydrogenated surfaces. • Bovine Serum Albumin proteins favored the surfaces with highest hydrogen content. • Surface modification induced secondary structure change of adsorbed proteins. - Abstract: We study the effect of amorphous silicon (a-Si) surface hydrogenation on Bovine Serum Albumin (BSA) adsorption. A set of (a-Si) films was prepared by radio frequency magnetron sputtering (RFMS) and after deposition; they were treated in molecular hydrogen ambient at different pressures (1–3 Pa). Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy and spectroscopic ellipsometry (SE) were used to study the hydrogenation effect and BSA adsorption. Atomic force microscopy (AFM) was used to evaluate morphological changes caused by hydrogenation. The wettability of the films was measured using contact angle measurement, and in the case of the hydrogenated surfaces, it was found to be driven by surface roughness. FTIR-ATR spectroscopy and SE measurements show that proteins had the strongest affinity toward the surfaces with the highest hydrogen content and their secondary structure was affected by a significant decrease of the α-helix component (-27%) compared with the proteins adsorbed on the un-treated surface, which had a predominantly α-helix (45%) structure. The adsorbed protein layer was found to be densely packed with a large thickness (30.9 nm) on the hydrogen-rich surfaces. The most important result is that the surface hydrogen content was the dominant factor, compared to wettability and morphology, for protein adsorption.

Highlights: • Hydrogenation of the surfaces had the effect of reducing the roughness by way of shadow etching. • Roughness was the driving factor affecting the wettability of the hydrogenated surfaces. • Bovine Serum Albumin proteins favored the surfaces with highest hydrogen content. • Surface modification induced secondary structure change of adsorbed proteins. - Abstract: We study the effect of amorphous silicon (a-Si) surface hydrogenation on Bovine Serum Albumin (BSA) adsorption. A set of (a-Si) films was prepared by radio frequency magnetron sputtering (RFMS) and after deposition; they were treated in molecular hydrogen ambient at different pressures (1–3 Pa). Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy and spectroscopic ellipsometry (SE) were used to study the hydrogenation effect and BSA adsorption. Atomic force microscopy (AFM) was used to evaluate morphological changes caused by hydrogenation. The wettability of the films was measured using contact angle measurement, and in the case of the hydrogenated surfaces, it was found to be driven by surface roughness. FTIR-ATR spectroscopy and SE measurements show that proteins had the strongest affinity toward the surfaces with the highest hydrogen content and their secondary structure was affected by a significant decrease of the α-helix component (-27%) compared with the proteins adsorbed on the un-treated surface, which had a predominantly α-helix (45%) structure. The adsorbed protein layer was found to be densely packed with a large thickness (30.9 nm) on the hydrogen-rich surfaces. The most important result is that the surface hydrogen content was the dominant factor, compared to wettability and morphology, for protein adsorption.

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

A novel boron nitride nanosheets (BNNSs)-amorphouscarbon (a-C) hybrid film has been deposited successfully on silicon substrates by simultaneous electrochemical deposition, and showed a good integrity of this B-C-N composite film by the interfacial bonding. This synthesis can potentially provide the facile control of the B-C-N composite film for the potential optoelectronic devices. This journal is

Short pulse laser damage and ablation of amorphous, diamond-like carbon films is investigated. Material removal is due to fracture of the film and ejection of large fragments, which exhibit a broadband emission of microsecond duration.

Hydrogenatedamorphous silicon (a-Si:H) as a large-area thin film semiconductor with ease of doping and low-cost fabrication capability has given a new impetus to the field of imaging sensors; its high radiation resistance also makes it a good material for radiation detectors. In addition, large-area microelectronics based on a-Si:H or polysilicon can be made with full integration of peripheral circuits, including readout switches and shift registers on the same substrate. Thin a-Si:H p-i-n photodiodes coupled to suitable scintillators are shown to be suitable for detecting charged particles, electrons, and X-rays. The response speed of CsI/a-Si:H diode combinations to individual particulate radiation is limited by the scintillation light decay since the charge collection time of the diode is very short (< 10ns). The reverse current of the detector is analyzed in term of contact injection, thermal generation, field enhanced emission (Poole-Frenkel effect), and edge leakage. A good collection efficiency for a diode is obtained by optimizing the p layer of the diode thickness and composition. The CsI(Tl) scintillator coupled to an a-Si:H photodiode detector shows a capability for detecting minimum ionizing particles with S/N ~20. In such an arrangement a p-i-n diode is operated in a photovoltaic mode (reverse bias). In addition, a p-i-n diode can also work as a photoconductor under forward bias and produces a gain yield of 3--8 for shaping times of 1 {micro}s. The mechanism of the formation of structured CsI scintillator layers is analyzed. Initial nucleation in the deposited layer is sensitive to the type of substrate medium, with imperfections generally catalyzing nucleation. Therefore, the microgeometry of a patterned substrate has a significant effect on the structure of the CsI growth.

For decades, the semiconductor industry has been steadily shrinking transistor sizes to fit more performance into a single silicon-based integrated chip. This technology has become the driving force for advances in education, transportation, and health, among others. However, transistor sizes are quickly approaching their physical limits (channel lengths are now only a few silicon atoms in length), and Moore's law will likely soon be brought to a stand-still despite many unique attempts to keep it going (FinFETs, high-k dielectrics, etc.). This technology must then be pushed further by exploring (almost) entirely new methodologies. Given the explosive growth of optical-based long-haul telecommunications, we look to apply the use of high-speed optics as a substitute to the digital model; where slow, lossy, and noisy metal interconnections act as a major bottleneck to performance. We combine the (nonlinear) optical Kerr effect with a single add-drop microring resonator to perform the fundamental AND-XOR logical operations of a half adder, by all-optical means. This process is also applied to subtraction, higher-order addition, and the realization of an all-optical arithmetic logic unit (ALU). The rings use hydrogenatedamorphous silicon as a material with superior nonlinear properties to crystalline silicon, while still maintaining CMOS-compatibility and the many benefits that come with it (low cost, ease of fabrication, etc.). Our method allows for multi-gigabit-per-second data rates while maintaining simplicity and spatial minimalism in design for high-capacity manufacturing potential.

Hydrogenatedamorphous silicon (a-Si:H) as a large-area thin film semiconductor with ease of doping and low-cost fabrication capability has given a new impetus to the field of imaging sensors; its high radiation resistance also makes it a good material for radiation detectors. In addition, large-area microelectronics based on a-Si:H or polysilicon can be made with full integration of peripheral circuits, including readout switches and shift registers on the same substrate. Thin a-Si:H p-i-n photodiodes coupled to suitable scintillators are shown to be suitable for detecting charged particles, electrons, and X-rays. The response speed of CsI/a-Si:H diode combinations to individual particulate radiation is limited by the scintillation light decay since the charge collection time of the diode is very short (< 10ns). The reverse current of the detector is analyzed in term of contact injection, thermal generation, field enhanced emission (Poole-Frenkel effect), and edge leakage. A good collection efficiency for a diode is obtained by optimizing the p layer of the diode thickness and composition. The CsI(Tl) scintillator coupled to an a-Si:H photodiode detector shows a capability for detecting minimum ionizing particles with S/N ∼20. In such an arrangement a p-i-n diode is operated in a photovoltaic mode (reverse bias). In addition, a p-i-n diode can also work as a photoconductor under forward bias and produces a gain yield of 3--8 for shaping times of 1 micros. The mechanism of the formation of structured CsI scintillator layers is analyzed. Initial nucleation in the deposited layer is sensitive to the type of substrate medium, with imperfections generally catalyzing nucleation. Therefore, the microgeometry of a patterned substrate has a significant effect on the structure of the CsI growth

Several deep level transient spectroscopy (DLTS) peaks (E42, E65, E75, E90, E262, and H180) are observed in n- and p-type Czochralski-grown Si samples subjected to hydrogenation by a dc H plasma treatment. The concentration of the defects is found to be proportional to the carbon and hydrogen content in our samples. The analysis of the depth profiles performed in Si samples hydrogenated by wet chemically etching shows that all these defects contain a single H atom. E65 and E75 appear only in samples with a high oxygen content which shows that oxygen is a constituent of these defects. The analysis of the enhancement of the emission rate of the defects with electric field shows that E65, E75, E90, and E262 are single acceptors whereas E42 is a double acceptor. The presence of a barrier for hole capture (about 53 meV) can explain the absence of the enhancement of the emission rate of H180, which can be attributed to a single acceptor state. From a comparison with theory, we assign E90 to CH1BC, E42 (E262) to CH1AB, and H180 to CH1Td. The similarity of the electrical properties of E65 and E75 to those of E90 suggest that E65 and E75 may originate from the CH1BC defect with an oxygen atom in its nearest neighborhood. Our results on the CH-related complexes give a conclusive explanation of some previously reported controversial experimental data.

This thesis deals with atmospheric contamination and cross-contamination of boron (single-chamber process) of the intrinsic absorber layer (i-layer) of p-i-n thin film solar cells based on hydrogenatedamorphous silicon. The atmospheric contaminations were introduced by means of intentional leaks. Hereby, the focus is on the influence of contamination species (oxygen and nitrogen), quantity of contamination (leak flow), source of contamination (leaks at chamber wall or in the process gas pipe), and plasma power on the properties of solar cells. Thereby, the minimum requirements for the purity of vacuum and process gas as well as leak conditions of the recipient and gas pipe system have been determined. Additionally, deposition regimes were developed, where the incorporation of impurities is significantly suppressed. For standard processes critical levels of nitrogen and oxygen contamination are determined to be {proportional_to} 4 x 10{sup 18} cm{sup -3} and {proportional_to} 2 x 10{sup 19} cm{sup -3}, respectively, for a leak situated at the chamber wall. Above these concentrations the solar cell efficiency deteriorates. In literature, incorporation of oxygen and nitrogen in doping configuration is assumed to be the reason for the cell deterioration. This assumption is supported by additional material studies of contaminated absorber layers done in this work. The difference in critical concentration is due to the higher doping efficiency of nitrogen compared to that for oxygen. Nevertheless, applying an air leak the critical concentrations of O and N are reached almost simultaneously since the incorporation probability of oxygen is about one order of magnitude higher compared to that for nitrogen. Applying a leak in the process gas pipe the critical oxygen contamination level increases to {proportional_to} 2 x 10{sup 20} cm{sup -3} whereas the critical nitrogen level remains unchanged compared to a chamber wall leak. Applying a deposition regime with a very high

Hydrogen storage materials based on the hydrogen spillover mechanism onto metal-doped nanoporous carbons are studied, in an effort to develop materials that store appreciable hydrogen at ambient temperatures and moderate pressures. We demonstrate that oxidation of the carbon surface can significantly increase the hydrogen uptake of these materials, primarily at low pressure. Trace water present in the system plays a role in the development of active sites, and may further be used as a strategy to increase uptake. Increased surface density of oxygen groups led to a significant enhancement of hydrogen spillover at pressures less than 100 milibar. At 300K, the hydrogen uptake was up to 1.1 wt. % at 100 mbar and increased to 1.4 wt. % at 20 bar. However, only 0.4 wt% of this was desorbable via a pressure reduction at room temperature, and the high lowpressure hydrogen uptake was found only when trace water was present during pretreatment. Although far from DOE hydrogen storage targets, storage at ambient temperature has significant practical advantages oner cryogenic physical adsorbents. The role of trace water in surface modification has significant implications for reproducibility in the field. High-pressure in situ characterization of ideal carbon surfaces in hydrogen suggests re-hybridization is not likely under conditions of practical interest. Advanced characterization is used to probe carbon-hydrogen-metal interactions in a number of systems and new carbon materials have been developed.

Full Text Available A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

Amorphous atomically flat diamond-like carbon (DLC) coatings were produced by direct ion deposition using a system based on a Penning ion source, butane precursor gas and post acceleration. Hydrogen depth profiles of the DLC coatings were measured with the 15N R-NRA method using the resonant nuclear reaction 1H(15N, αγ)12C (Eres = 6.385 MeV). The films produced at 3.0-10.5 kV acceleration voltage show two main effects. First, compared to average elemental composition of the film, the near-surface region is hydrogen depleted. The increase of the hydrogen concentration by 3% from the near-surface region towards the bulk is attributed to a growth model which favours the formation of sp2 hybridised carbon rich films in the film formation zone. Secondly, the depth at which the maximum hydrogen concentration is measured increases with acceleration voltage and is proportional to the penetration depth of protons produced by the ion source from the precursor gas. The observed effects are explained by a deposition process that takes into account the contributions of ion species, hydrogen effusion and preferential displacement of atoms during direct ion deposition.

Amorphous atomically flat diamond-like carbon (DLC) coatings were produced by direct ion deposition using a system based on a Penning ion source, butane precursor gas and post acceleration. Hydrogen depth profiles of the DLC coatings were measured with the 15N R-NRA method using the resonant nuclear reaction {sup 1}H({sup 15}N, αγ){sup 12}C (E{sub res} = 6.385 MeV). The films produced at 3.0–10.5 kV acceleration voltage show two main effects. First, compared to average elemental composition of the film, the near-surface region is hydrogen depleted. The increase of the hydrogen concentration by 3% from the near-surface region towards the bulk is attributed to a growth model which favours the formation of sp{sup 2} hybridised carbon rich films in the film formation zone. Secondly, the depth at which the maximum hydrogen concentration is measured increases with acceleration voltage and is proportional to the penetration depth of protons produced by the ion source from the precursor gas. The observed effects are explained by a deposition process that takes into account the contributions of ion species, hydrogen effusion and preferential displacement of atoms during direct ion deposition.

Various forms of carbon are known to perform well as biomaterials in a variety of applications and an improved understanding of their interactions with biomolecules, cells, and tissues is of interest for improving and tailoring their performance. Nanoplasmonic sensing (NPS) has emerged as a powerful technique for studying the thermodynamics and kinetics of interfacial reactions. In this work, the in situ adsorption of two proteins, bovine serum albumin and fibrinogen, were studied at carbon surfaces with differing chemical and optical properties using nanoplasmonic sensors. The carbon material was deposited as a thin film onto NPS surfaces consisting of 100 nm Au nanodisks with a localized plasmon absorption peak in the visible region. Carbon films were fully characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and spectroscopic ellipsometry. Two types of material were investigated: amorphouscarbon (a-C), with high graphitic content and high optical absorptivity, and hydrogenatedamorphouscarbon (a-C:H), with low graphitic content and high optical transparency. The optical response of the Au/carbon NPS elements was modeled using the finite difference time domain (FDTD) method, yielding simulated analytical sensitivities that compare well with those observed experimentally at the two carbon surfaces. Protein adsorption was investigated on a-C and a-C:H, and the protein layer thicknesses were obtained from FDTD simulations of the expected response, yielding values in the 1.8-3.3 nm range. A comparison of the results at a-C and a-C:H indicates that in both cases fibrinogen layers are thicker than those formed by albumin by up to 80%.

Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphoushydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author)

PAHs can have several forms in the interstellar medium. To assess the importance of each requires the availability of a collection of high quality, complete mid-ir interstellar emission spectra, a collection of laboratory spectra of PAH samples prepared under realistic conditions and a firm understanding of the microscopic emission mechanism. Given what we currently know about PAHs, the spectroscopic data suggests that there are at least two components which contribute to the interstellar emission spectrum: free molecule sized PAHs producing the narrow features and amorphouscarbon particles (which are primarily made up of an irregular ''lattice'' of PAHs) contributing to the broad underlying components. An exact treatment of the ir fluorescence from highly vibrationally excited large molecules shows that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphouscarbon particles. Since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is called for in conjunction with an observational program which focuses on the spatial characteristics of the spectra. In this way the distribution and evolution of carbon from molecule to particle can be traced. 38 refs., 9 figs

Battery research has been going full steam and with that the search for alternative anodes. Among many proposed electrode materials, little attention has been given to phosphorus. Phosphorus boasts the third highest gravimetric charge capacity and the highest volumetric charge capacity of all elements. Because of that, it would be an attractive battery anode material were it not for its poor cyclability with significant capacity loss immediately after the first cycle. This is known to be the consequence of considerable volume changes of phosphorus during charge/discharge cycles. In this work, we propose circumventing this issue by mixing amorphous red phosphorus with carbon nanotubes. By employing a non-destructive sublimation-deposition method, we have synthesized composites where the synergetic effect between phosphorus and carbon nanotubes allow for an improvement in the electrochemical performance of battery anodes. In fact, it has been shown that carbon nanotubes can act as an effective buffer to phosphorus volumetric expansions and contractions during charging and discharging of the half-cells [1]. By modifying the synthesis parameters, we have also been able to change the degree of crystallinity of the phosphorus matrix in the composites. In fact, the less common phase of red phosphorus, named fibrous phosphorus, was obtained, and that explains some of the varying electrochemical performances observed in the composites. Overall, it is found that a higher surface area of amorphous phosphorus allows for a better anode material when using single-walled carbon nanotubes as fillers.

A novel superhydrophobic ternary graphene/amorphouscarbon/nickel (G-Ni/a-C:H) carbon-based film was fabricated by a green approach of high-voltage electrochemical deposition without using aqueous solution, which was systematically investigated including the structure and relating applications on self-cleaning and corrosion resistance. Graphene and nickel nano-particle inserts were effective to tailor the feature of nanocrystallite/amorphous microstructure as well as micro-nanoscale hierarchical rose-petal-like surface for G-Ni/a-C:H carbon-based film. Surprisingly, this deposit could present outstanding superhydrophobicity with the contact angle of 158.98 deg and sliding angle of 2.75 deg without any further surface modification meanwhile it could possess fairly well adhesion. Furthermore, the superhydrophobic G-Ni/a-C:H carbon-based film could exhibit excellent corrosion resistance and self-cleaning performances compared to no graphene incorporated deposit. The procedure of fabricating deposit might be simple, scalable, and environmental friendly, indicating a promising prospect for industrial applications in the field of anti-fouling, anti-corrosion and drag resistance.

The goal of this work was the study, development and optimization of hydrogenatedamorphous silicon (a-Si:H) devices for use in detection of ionizing radiation in applications connected to the nuclear industry. Thick p-i-n devices, capable of withstanding large electric fields (up to 10 6 V/cm) with small currents (nA/cm 2 ), were proposed and developed. In order to decrease fabrication time, films were made using the 'He diluted' PECVD process and compared to standard a-Si:H films. Aspects connected to specific detector applications as well as to the fundamental physics of a-Si:H were considered: the internal electric field technique, in which the depletion charge was measured as a function of the applied bias voltage; study of the leakage current of p-i-n devices permitted us to demonstrate different regimes: depletion, field-enhanced thermal generation and electronic injection across the p layer. The effect of the electric field on the thermal generation of the carriers was studied considering the Poole-Frenkel and tunneling mechanisms. A model was developed taking under consideration the statistics of the correlated states and electron-phonon coupling. The results suggest that mechanisms not included in the 'standard model' of a Si:h need to be considered, such as defect relaxation, a filed-dependent mobility edge etc...; a new metastable phenomenon, called 'forming', induced by prolonged exposure to a strong electric field, was observed and studied. It is characterized by marked decrease of the leakage current and the detector noise, and increase in the breakdown voltage, as well as an improvement of carrier collection efficiency. This forming process appears to be principally due to an activation of the dopants in the p layer; finally, the capacity of thick p-i-n a Si:H devices to detect ionizing radiation has been evaluated. We show that it is possible, with 20-50 micron thick p-i-n devices, to detect the full spectrum of alpha and beta particles. With an

Full Text Available As diamond like carbon (DLC coating becomes increasingly popular in providing low friction and wear under lubricated conditions, the effect of various oil additives on tribological behavior of DLC coating is drawing more attention. Various oil additives, such as ZnDTP and MoDTC, have been widely used in automobile engine industry to pursuit excellent tribological performance in the insufficient lubrication condition. Although such commercial oil additives have been proven to reduce friction or/and wear to some extent, usage of such high -SAPS (sulphuric ash, phosphor, sulfphur conventional additives is bound to arouse concerns due to environmental reasons. In this research, we investigate the effect of two nanoparticle oil additives, which are cerium oxide (CeO2 and zirconium dioxide (ZrO2, on friction and wear of non-hydrogen tetrahedral amorphouscarbon (ta-C coating. The results show that by adding ZrO2 nanoparticle, the friction of DLC coating could be reduced about 32% compared to non-additive base oil scenario, but specific wear rate increases by 40%. When CeO2 nanoparticle is used, friction increases by 22% compared to non-additive base oil scenario, however wear decreases by nearly 77%.

Full Text Available Hydrogenatedamorphous silicon thin film tandem solar cells (a-Si:H/a-Si:H have been developed with focus on high open-circuit voltages for the direct application as photocathodes in photoelectrochemical water splitting devices. By temperature variation during deposition of the intrinsic a-Si:H absorber layers the band gap energy of a-Si:H absorber layers, correlating with the hydrogen content of the material, can be adjusted and combined in a way that a-Si:H/a-Si:H tandem solar cells provide open-circuit voltages up to 1.87 V. The applicability of the tandem solar cells as photocathodes was investigated in a photoelectrochemical cell (PEC measurement set-up. With platinum as a catalyst, the a-Si:H/a-Si:H based photocathodes exhibit a high photocurrent onset potential of 1.76 V versus the reversible hydrogen electrode (RHE and a photocurrent of 5.3 mA/cm2 at 0 V versus RHE (under halogen lamp illumination. Our results provide evidence that a direct application of thin film silicon based photocathodes fulfills the main thermodynamic requirements to generate hydrogen. Furthermore, the presented approach may provide an efficient and low-cost route to solar hydrogen production.

It is reported the synthesis and characterization of thin films of amorphouscarbon (a-C) nitrided, deposited by laser ablation in a nitrogen atmosphere at pressures which are from 4.5 x 10 -4 Torr until 7.5 x 10 -2 Torr. The structural properties of the films are studied by Raman spectroscopy obtaining similar spectra at the reported for carbon films type diamond. The study of behavior of the energy gap and the ratio nitrogen/carbon (N/C) in the films, shows that the energy gap is reduced when the nitrogen incorporation is increased. It is showed that the refraction index of the thin films diminish as nitrogen pressure is increased, indicating the formation of graphitic material. (Author)

High-resolution transmission electron microscopy (HRTEM) shows that amorphous-tetrahedral diamondlike carbon (a-tC) films grown by pulsed-laser deposition on Si(100) consist of three-to-four layers, depending on the growth energetics. We estimate the density of each layer using both HRTEM image contrast and Rutherford backscattering spectrometry. The first carbon layer and final surface layer have relatively low density. The bulk of the film between these two layers has higher density. For films grown under the most energetic conditions, there exists a superdense a-tC layer between the interface and bulk layers. The density of all four layers, and the thickness of the surface and interfacial layers, correlate well with the energetics of the depositing carbon species.

Due to unique structural, mechanical and electrical properties of single wall carbon nanotubes, SWNTs, they have been proposed as promising hydrogen storage materials especially in automotive industries. This research deals with investing of CNT's and some activated carbonshydrogen storage capacity. The CNT's were prepared through natural gas decomposition at a temperature of 900 C over cobalt-molybdenum nanoparticles supported by nanoporous magnesium oxide (Co-Mo/MgO) during a chemical vapor deposition (CVD) process. The effects of purity of CNT (80-95%wt.) on hydrogen storage were investigated here. The results showed an improvement in the hydrogen adsorption capacity with increasing the purity of CNT's. Maximum adsorption capacity was 0.8%wt. in case of CNT's with 95% purity and it may be raised up with some purification to 1%wt. which was far less than the target specified by DOE (6.5%wt.). Also some activated carbons were manufactured and the results compared to CNTs. There were no considerable H{sub 2}-storage for carbon nanotubes and activated carbons at room-temperature due to insufficient binding between H{sub 2} molecules carbon nanostructures. Therefore, hydrogen must be adsorbed via interaction of atomic hydrogen with the storage environment in order to achieve DOE target, because the H atoms have a very stronger interaction with carbon nanostructures. (author)

Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT.

Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT.

Physisorption of molecular hydrogen on single-walled carbon nanotubes (SWCNTs) is important for its engineering applications and hydrogen energy storage. Using molecular dynamics simulation, we study the physisorption of molecular hydrogen on a SWCNT with a vacant defect, focusing on the effect of the vacant defect size and external parameters such as temperature and pressure. We find that hydrogen can be physisorbed inside a SWCNT through a vacant defect when the defect size is above a threshold. By controlling the size of the defects, we are able to extract hydrogen molecules from a gas mixture and store them inside the SWCNT. We also find that external parameters, such as low temperature and high pressure, enhance the physisorption of hydrogen molecules inside the SWCNT. In addition, the storage efficiency can be improved by introducing more defects, i.e., reducing the number of carbon atoms on the SWCNT

Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained. During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature (T room ), 100 deg. C, 150 deg. C and 200 deg. C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films. Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 deg. C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 ± 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the I D /I G or sp 3 /sp 2 ratio and not by the absolute sp 3 or sp 2 concentration.

Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained. During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature (T{sub room}), 100 deg. C, 150 deg. C and 200 deg. C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films. Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 deg. C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 {+-} 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the I{sub D}/I{sub G} or sp{sup 3}/sp{sup 2} ratio and not by the absolute sp{sup 3} or sp{sup 2} concentration.

Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO3 core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.

Recent developments aiming at the accelerated commercialization of fuel cells for automotive applications have triggered an intensive research on fuel storage concepts for fuel cell cars. The fuel cell technology currently lacks technically and economically viable hydrogen storage technologies. On-board reforming of gasoline or methanol into hydrogen can only be regarded as an intermediate solution due to the inherently poor energy efficiency of such processes. Hydrogen storage in carbon nanofibers may lead to an efficient solution to the above described problems.

Dual ion implantation of titanium and carbon was shown to produce an amorphous layer of exceptional strength within annealed bulk Ni and electroformed Ni and Ni 80 Fe 20 materials used in micro-electromechanical systems. The intrinsic elastic and plastic mechanical properties of the implanted region were quantified using nanoindentation testing in conjunction with finite-element modeling, and the results were interpreted in the light of microstructures observed by electron microscopy. The implantation treatment was found to produce substantial reductions in unlubricated friction and wear

Using density functional theory and molecular dynamics we found that N-decorated single walled (8,0) carbon nanotubes are potential high capacity hydrogen storage media. This system could store up to 6.0 wt% hydrogen at 300 K and ambient pressure, with average adsorption energy of -80 meV/(H 2 ). Nitrogen coverage was C 8 N.

Hydrogenatedamorphous silicon germanium films (a-SiGe:H) and devices have been extensively studied because of the tunable band gap for matching the solar spectrum and mature the fabrication techniques. a-SiGe:H thin film solar cells have great potential for commercial manufacture because of very low cost and adaptability to large-scale manufacturing. Although it has been demonstrated that a-SiGe:H thin films and devices with good quality can be produced successfully, some issues regarding growth chemistry have remained yet unexplored, such as the hydrogen and inert-gas dilution, bombardment effect, and chemical annealing, to name a few. The alloying of the SiGe introduces above an order-of-magnitude higher defect density, which degrades the performance of the a-SiGe:H thin film solar cells. This degradation becomes worse when high growth-rate deposition is required. Preferential attachment of hydrogen to silicon, clustering of Ge and Si, and columnar structure and buried dihydride radicals make the film intolerably bad. The work presented here uses the Electron-Cyclotron-Resonance Plasma-Enhanced Chemical Vapor Deposition (ECR-PECVD) technique to fabricate a-SiGe:H films and devices with high growth rates. Helium gas, together with a small amount of H2, was used as the plasma species. Thickness, optical band gap, conductivity, Urbach energy, mobility-lifetime product, I-V curve, and quantum efficiency were characterized during the process of pursuing good materials. The microstructure of the a-(Si,Ge):H material was probed by Fourier-Transform Infrared spectroscopy. They found that the advantages of using helium as the main plasma species are: (1) high growth rate--the energetic helium ions break the reactive gas more efficiently than hydrogen ions; (2) homogeneous growth--heavy helium ions impinging on the surface promote the surface mobility of the reactive radicals, so that heteroepitaxy growth as clustering of Ge and Si, columnar structure are

Thin-film silicon allows the fabrication of MEMS devices at low processing temperatures, compatible with monolithic integration in advanced electronic circuits, on large-area, low-cost, and flexible substrates. The most relevant thin-film properties for applications as MEMS structural layers are the deposition rate, electrical conductivity, and mechanical stress. In this work, n + -type doped hydrogenatedamorphous and nanocrystalline silicon thin-films were deposited by RF-PECVD, and the influence of the hydrogen dilution in the reactive mixture, the RF-power coupled to the plasma, the substrate temperature, and the deposition pressure on the structural, electrical, and mechanical properties of the films was studied. Three different types of silicon films were identified, corresponding to three internal structures: (i) porous amorphous silicon, deposited at high rates and presenting tensile mechanical stress and low electrical conductivity, (ii) dense amorphous silicon, deposited at intermediate rates and presenting compressive mechanical stress and higher values of electrical conductivity, and (iii) nanocrystalline silicon, deposited at very low rates and presenting the highest compressive mechanical stress and electrical conductivity. These results show the combinations of electromechanical material properties available in silicon thin-films and thus allow the optimized selection of a thin silicon film for a given MEMS application. Four representative silicon thin-films were chosen to be used as structural material of electrostatically actuated MEMS microresonators fabricated by surface micromachining. The effect of the mechanical stress of the structural layer was observed to have a great impact on the device resonance frequency, quality factor, and actuation force

Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and

Highlights: • The hydrogen adsorption of lithium-doped KOH activated carbons has been studied. • Lithium doping improves their hydrogen adsorption affinity. • Lithium doping is more effective for materials with micropores of 0.8 nm or smaller. • Lithium reagent can alter the pore structure, depending on the raw material. • Optimizing the pore size and functional group is needed for better hydrogen uptake. - Abstract: The authors have studied the hydrogen adsorption performance of several types of lithium-doped KOH activated carbons. In the case of activated cokes, lithium doping improves their hydrogen adsorption affinity from 5.02 kg/m 3 to 5.86 kg/m 3 at 303 K. Hydrogen adsorption density increases by around 17% after lithium doping, likely due to the fact that lithium doping is more effective for materials with micropores of 0.8 nm or smaller. The effects of lithium on hydrogen storage capacity vary depending on the raw material, because the lithium reagent can react with the material and alter the pore structure, indicating that lithium doping has the effect of plugging or filling the micropores and changing the structures of functional groups, resulting in the formation of mesopores. Despite an observed decrease in hydrogen uptake, lithium doping was found to improve hydrogen adsorption affinity. Lithium doping increases hydrogen uptake by optimizing the pore size and functional group composition

Cocrystals and amorphous solid dispersions have generated interest in the pharmaceutical industry as an alternative to more established solid delivery forms. The identification of intermolecular hydrogen bonding interactions in a nicotinamide palmitic acid cocrystal and a 50% w/w acetaminophen-polyvinylpyrrolidone solid dispersion are reported using advanced solid-state magic-angle spinning (MAS) NMR methods. The application of a novel (14)N-(1)H HMQC experiment, where coherence transfer is achieved via through-space couplings, is shown to identify specific hydrogen bonding motifs. Additionally, (1)H isotropic chemical shifts and (14)N electric field gradient (EFG) parameters, both accessible from (14)N-(1)H HMQC experiments, are shown to be sensitive to changes in hydrogen bonding geometry. Numerous indicators of molecular association are accessible from this experiment, including NH cross-peaks occurring from intermolecular hydrogen bonds and changes in proton chemical shifts or electric field gradient parameters. First-principles calculations using the GIPAW approach that yield accurate estimates of isotropic chemical shifts, and EFG parameters were used to assist in assignment. It is envisaged that (14)N-(1)H HMQC solid state NMR experiments could become a valuable screening technique of solid delivery forms in the pharmaceutical industry.

The adsorption of Bovine Serum Albumin (BSA) proteins on amorphous silicon (a-Si) surfaces was studied with respect to solution pH. Thin films of a-Si were deposited using radio-frequency magnetron sputtering at room temperature and then treated in a hydrogen ambient to form a hydrogenated a-Si surface layer (a-Si:H). The interactions of the as-deposited and hydrogenated surfaces with the proteins at neutral, acidic, and basic environments was probed by means of Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy, Spectroscopic Ellipsometry (SE), and Atomic Force Microscopy (AFM), to study the influence of the charge of proteins on their adsorption and conformation on the a-Si:H surface, compared with the a-Si surface. The results show that the charge of the proteins has a significant effect on their interactions with these two substrates but in dissimilar ways. For the as-deposited substrate, these interactions are predictably coulombic since the surface is charged. For the hydrogenated substrate, the adsorption of the proteins depends on their conformation which is heavily affected by pH, and the size of their footprint (adsorption mode) on the surface.

Full Text Available We investigate the structural, mechanical, and electronic properties of graphite-like amorphouscarbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1–16 eV. As the incident energy decreases, the ratio of sp2 carbons increases, that of sp3 decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries.

We present a moderate resolution H I map of the amorphous galaxy NGC 4670. Our previous lower resolution data had shown a symmetric H I distribution centered on the single supergiant H II region and highly concentrated to the center of the galaxy. We now resolve the central H I distribution into

In this paper we study the reflection, absorption, and transmission of microwave from nonuniform hydrogen gas in carbon nanotubes, grown by iron-catalyzed high-pressure carbon monoxide disproportionate (HiPco) process. A discussion on the effect of various hydrogen gas parameters on the reflected power, absorbed power, and transmitted power is presented. The nonuniform hydrogen gas slab is modeled by a series of subslabs. The overall number density profile across the whole slab follows a parabolic function. The total reflected, absorbed, and transmitted powers are then deduced and their functional dependence on the number density, collision frequency, and angle of propagation is studied

We report a procedure to implant high dose of xenon atoms (Xe) in amorphouscarbon, a-C, and amorphous silicon, a-Si, for application in brachytherapy seeds. An ion beam assisted deposition (IBAD) system was used for the deposition of the films, where one ion gun was used for sputtering a carbon (or silicon) target, while the other ion gun was used to simultaneously bombard the growing film with a beam of xenon ion Xe + in the 0–300 eV range. Xe atoms were implanted into the film with concentration up to 5.5 at.%, obtained with Xe bombardment energy in the 50–150 eV range. X-ray absorption spectroscopy was used to investigate the local arrangement of the implanted Xe atoms through the Xe L III absorption edge (4.75 keV). It was observed that Xe atoms tend to agglomerate in nanoclusters in a-C and are dispersed in a-Si.

Amorphouscarbon nitride thin films were deposited on polymer substrates using radio frequency (rf) plasma in a mixture of nitrogen (N{sub 2}) and acetylene (C{sub 2}H{sub 2}) gasses. The samples were prepared at different rf plasma power (350, 400, 450, 500, and 550 W), at constant plasma exposure time of 10 min, and constant N{sub 2}/C{sub 2}H{sub 2} ratio of 50%. The crystal structure and surface morphology of the prepared samples were examined using X-ray diffraction and atomic force microscopy analysis, respectively. The absence of the carbon nitride diffraction peaks confirms the amorphous nature of these films. The root mean square roughness of the films increased from 3.77 to 25.22 nm as the power increased from 350 to 550 W. The thickness and the deposition rate were found to increase with increasing plasma power. Over the whole studied wavelength range, from 200 to 2500 nm, the transmittance decreased with increasing plasma power. A shift in the onset of absorption towards higher wavelengths with increasing plasma power, indicating a decrease in the optical band gap, has been observed. The refractive index values were found to decrease while the extinction coefficient increased with increasing plasma power.

Amorphouscarbon nitride thin films were deposited on polymer substrates using radio frequency (rf) plasma in a mixture of nitrogen (N 2) and acetylene (C 2H 2) gasses. The samples were prepared at different rf plasma power (350, 400, 450, 500, and 550 W), at constant plasma exposure time of 10 min, and constant N 2/C 2H 2 ratio of 50%. The crystal structure and surface morphology of the prepared samples were examined using X-ray diffraction and atomic force microscopy analysis, respectively. The absence of the carbon nitride diffraction peaks confirms the amorphous nature of these films. The root mean square roughness of the films increased from 3.77 to 25.22 nm as the power increased from 350 to 550 W. The thickness and the deposition rate were found to increase with increasing plasma power. Over the whole studied wavelength range, from 200 to 2500 nm, the transmittance decreased with increasing plasma power. A shift in the onset of absorption towards higher wavelengths with increasing plasma power, indicating a decrease in the optical band gap, has been observed. The refractive index values were found to decrease while the extinction coefficient increased with increasing plasma power.

The objective of this work is the synthesis and characterization of thin films of amorphouscarbon (a-C) and thin films of nitrided amorphouscarbon (a-C-N) using the laser ablation technique for their deposit. For this purpose, the physical properties of the obtained films were studied as function of diverse parameters of deposit such as: nitrogen pressure, power density, substrate temperature and substrate-target distance. For the characterization of the properties of the deposited thin films the following techniques were used: a) Raman spectroscopy which has demonstrated being a sensitive technique to the sp 2 and sp 3 bonds content, b) Energy Dispersive Spectroscopy which allows to know semi-quantitatively way the presence of the elements which make up the deposited films, c) Spectrophotometry, for obtaining the absorption spectra and subsequently the optical energy gap of the deposited material, d) Ellipsometry for determining the refraction index, e) Scanning Electron Microscopy for studying the surface morphology of thin films and, f) Profilemetry, which allows the determination the thickness of the deposited thin films. (Author)

distribution models, and gamma response models was developed. This software can be used for direct numerical comparison between the models, submodels and their parameters and experimental data. In the present paper, we look at 10%-survival data from cell lines irradiated in vitro with carbon and proton beams...... neutrons, stopped pions, and heavy ion beams. Nucl Instrum Meth. 1973;111:93-116. 2.Weyrather WK, Kraft G. RBE of carbon ions: experimental data and the strategy of RBE calculation for treatment planning. Radiother Oncol. 2004;73(Suppl 2):161-9. 3.Greilich S, Grzanka L, Bassler N, Andersen CE, Jäkel O...... irradiation. The aim of this paper is to compare the predictions from different amorphous approaches found in the literature - more specifically the phenomenological, analytical model by Katz and co-workers [1] and a Monte-Carlo based full as implemented for example in the local effect model by Scholz et al...

Full Text Available Abstract The electrical behavior of multi-walled carbon nanotube network embedded in amorphous silicon nitride is studied by measuring the voltage and temperature dependences of the current. The microstructure of the network is investigated by cross-sectional transmission electron microscopy. The multi-walled carbon nanotube network has an uniform spatial extension in the silicon nitride matrix. The current-voltage and resistance-temperature characteristics are both linear, proving the metallic behavior of the network. The I-V curves present oscillations that are further analyzed by computing the conductance-voltage characteristics. The conductance presents minima and maxima that appear at the same voltage for both bias polarities, at both 20 and 298 K, and that are not periodic. These oscillations are interpreted as due to percolation processes. The voltage percolation thresholds are identified with the conductance minima.

Amorphous carbonaceous char produced from the pyrolysis of polymer solids has many desirable properties for ablative heat shields for space vehicles. Molecular dynamics simulations are presented to study the transformation of the local atomic structure from virgin polymer to a dense, disordered char [1]. Release of polymer hydrogen is found to be critical to allow the system to collapse into a highly coordinated char structure. Mechanisms of the char formation process and the morphology of the resulting structures are elucidated. Thermal conductivity and mechanical response of the resulting char are evaluated [2]. During reenty, the optical response and oxidative reactivity of char are also important properties. Results of ab initio computations of char optical functions [3] and char reactivity [4] are also presented.

The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H2O2) using amorphouscarbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H2O2 (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphouscarbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8%, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9%, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9 ± 2 and 85.5 ± 2 %, whereas 70% of total organic carbon removal was achieved.

The formation of Mg-bearing calcite via an amorphous precursor is a poorly understood process that is of relevance for biogenic and abiogenic carbonate precipitation. In order to gain an improved insight on the controls of Mg incorporation in calcite formed via an Mg-rich amorphous calcium carbonate (Mg-ACC) precursor, the precipitation of Mg-ACC and its transformation to Mg-calcite was monitored by in situ Raman spectroscopy. The experiments were performed at 25.0 ± 0.03 °C and pH 8.3 ± 0.1 and revealed two distinct pathways of Mg-calcite formation: (i) At initial aqueous Mg/Ca molar ratios ⩽ 1:6, Mg-calcite formation occurs via direct precipitation from solution. (ii) Conversely, at higher initial Mg/Ca molar ratios, Mg-calcite forms via an intermediate Mg-rich ACC phase. In the latter case, the final product is a calcite with up to 20 mol% Mg. This Mg content is significant higher than that of the Mg-rich ACC precursor phase. Thus, a strong net uptake of Mg ions from the solution into the crystalline precipitate throughout and also subsequent to ACC transformation is postulated. Moreover, the temporal evolution of the geochemical composition of the reactive solution and the Mg-ACC has no significant effect on the obtained ;solubility product; of Mg-ACC. The enrichment of Mg in calcite throughout and subsequent to Mg-ACC transformation is likely affected by the high aqueous Mg/Ca ratio and carbonate alkalinity concentrations in the reactive solution. The experimental results have a bearing on the formation mechanism of Mg-rich calcites in marine early diagenetic environments, where high carbonate alkalinity concentrations are the rule rather than the exception, and on the insufficiently investigated inorganic component of biomineralisation pathways in many calcite secreting organisms.

The solar energy is the largest energy source in the world. Using the photosynthesis, we will be able utilise the huge amount of carbon dioxide. Microalgae, cyanobacteria, photosynthetic bacteria belong to photosynthetic microorganisms, which assimilate carbon dioxide during the photosynthesis. One of the cyanobacteria, Spirulina platensis accumulates carbohydrate photoautotrophically up to 50% of the dry cell weight in the nitrogen-deficient condition. Under an anaerobic condition in the dark, it is degraded into organic compounds such as organic acids, alcohol and sugar. As the hydrogen gas is also evolved in this process, the participation of hydrogenase (Hydrogen producing enzyme) has been suggested in this metabolism. We have investigated several conditions of evolution of hydrogen and production of organic compounds. The bacterial concentration initial pH and temperature had significant effects on hydrogen evolution as well as production of organic compounds. When the bacterial cell concentration was high, the pH of fermentation products was reduced to acidic and the evolution of hydrogen tended to be inhibited. The profiles of fermentation products varied according to the culture condition. The increase of organic acids were remarkable in the inhibitory condition for hydrogen production, such as acidic pH and high temperature. Furthermore these fermentation products were converted into hydrogen gas by using photosynthetic bacterium Rhodobacter sphaeroides RV with light energy. The composition of evolved gas was mainly hydrogen and carbon dioxide, and their contents were 78% and 10%, respectively. The total amount of evolved hydrogen was nearly equal to the estimated, value which was calculated by the degradation of each organic acid. Combining this system with the photosynthesis of cyanobacteria, we could accomplish the production of hydrogen by solar energy, carbon dioxide and water. And we demonstrated that the evolved gas could be directly supplied to the

Here we report on the results of an in situ X-ray diffraction study of phase transformations during catalytic graphitisation of amorphouscarbon. It is demonstrated that there is unusual change of iron catalyst reflection intensity at low temperature approx 640 deg. C. This unusual intensity change may possibly be caused by the transition of some part of metal into liquid state at low temperature. It was also shown by electron microscopy that although no graphite reflections were detected 80-90% of amorphouscarbon becomes graphite after sample heating in a high temperature vacuum chamber.

Provided herein are genetically engineered microbes that include at least a portion of a carbon fixation pathway, and in one embodiment, use molecular hydrogen to drive carbon dioxide fixation. In one embodiment, the genetically engineered microbe is modified to convert acetyl CoA, molecular hydrogen, and carbon dioxide to 3-hydroxypropionate, 4-hydroxybutyrate, acetyl CoA, or the combination thereof at levels greater than a control microbe. Other products may also be produced. Also provided herein are cell free compositions that convert acetyl CoA, molecular hydrogen, and carbon dioxide to 3-hydroxypropionate, 4-hydroxybutyrate, acetyl CoA, or the combination thereof. Also provided herein are methods of using the genetically engineered microbes and the cell free compositions.

The goal of this work is to study the properties of the defects aiming to explore the types of defects and the effect of various deposition parameters such as substrate temperature, the kind of the substrate, gas pressure and deposition rate. Two kinds of samples have been used; The first one was a series of Schottky diodes, and the second one a series of solar cells (p-i-n junction) deposited on crystalline silicon or on corning glass substrates with different deposition parameters. The deposition parameters were chosen to obtain materials whose their structures varying from amorphous to microcrystalline silicon including polymorphous silicon. Our results show that the polymorphous silicon samples deposited at high deposition rates present the best photovoltaic properties in comparison with those deposited at low rates. Also we found that the defects concentration in high deposition rate samples is less at least by two orders than that obtained in low deposition rate polymorphous, microcrystalline and amorphous samples. This study shows also that there is no effect of the substrate, or the thin films of highly doped amorphous silicon deposited on the substrate, on the creation and properties of these defects. Finally, different experimental methods have been used; a comparison between their results has been presented. (author)

Carbon-tungsten co-deposition layers (C-W layers) were formed by sputtering method using hydrogen or deuterium RF plasma. The deposition rate of the C-W layer by deuterium plasma was faster than that by hydrogen plasma, where the increase of deposition rate of tungsten was larger than that of carbon. This indicates that the isotope effect on sputtering-depositing process for tungsten is larger than that for carbon. The release curve of hydrogen from the C-W layer showed two peaks at 400 deg. C and 700 deg. C. Comparing the hydrogen release from the carbon deposition layer and the tungsten deposition layer, it is considered that the increase of the release rate at 400 deg. C is affected by tungsten and that at 700 deg. C is affected by carbon. The obtained hydrogen retention in the C-W layers which have over 60 at.% of carbon was in the range between 0.45 and 0.16 as H/(C + W)

Composites with micro-sized magnetic particles dispersed in amorphouscarbon were fabricated conveniently and economically by carbonizing polyacrylonitrile (PAN) fibers mixed with micro-sized iron particles under different temperatures. The composites were characterized by X-ray diffraction (XRD) and scanning electric microscope (SEM). The electromagnetic (EM) properties were measured by a vector network analyzer in the frequency range of 2–18 GHz based on which analog computations of EM wave absorption properties were carried out. The influences of temperature on phase composition and EM wave absorption properties were also investigated, indicating that the composites had good electromagnetic absorption properties with both electrical loss and magnetic loss. Effective reflection loss (RLamorphous carbon. • The influences of temperature on phase composition and electromagnetic wave absorption properties were investigated. • The composites heated up to 750 °C and 800 °C had good electromagnetic wave absorption property.

The amorphous alumina phosphors without containing expensive or toxic elements were prepared via a solution method. The obtained sample indicates bluish-white emission centered at 390–430 nm by UV excitation. According to the measurement results of Electron Spin Resonance (ESR), Fourier Transform Infrared Spectroscopy (FT-IR) and organic microanalysis, it is found that the carbon impurities exist in the sample and they are essential for luminescence. On the other hand, {sup 27}Al NMR measurements indicate the presence of Al of 5-coordination. Moreover, there is good correspondence among the excitation spectra of the emission samples, the experimental optical properties of amorphous alumina, and the calculated oxygen vacancies levels in amorphous alumina model. Therefore, the new luminescence mechanism can be proposed as follows; the electrons in valence band are excited to oxygen vacancies bands by UV light and return to ground state through the carbon impurities band, being accompanied by the bluish-white emission. - Highlights: • The amorphous alumina prepared via solution method shows bluish-white emission. • According to the ESR results, carbon impurities are necessary for luminescence. • FT-IR, NMR and UV–vis measurements of the samples were conducted. • Our results indicated that oxygen vacancies play an important role. • We proposed the new luminescence mechanism for amorphous alumina phosphor.

Full Text Available Raman spectroscopy is a most often used standard technique for characterization of different carbon materials. In this work we present the Raman spectra of polycrystalline diamond layers of different quality, synthesized by Hot Filament Chemical Vapor Deposition method (HF CVD. We show how to use Raman spectroscopy for the analysis of the Raman bands to determine the structure of diamond films as well as the structure of amorphouscarbon admixture. Raman spectroscopy has become an important technique for the analysis of CVD diamond films. The first-order diamond Raman peak at ca. 1332 cm−1 is an unambiguous evidence for the presence of diamond phase in the deposited layer. However, the existence of non-diamond carbon components in a CVD diamond layer produces several overlapping peaks in the same wavenumber region as the first order diamond peak. The intensities, wavenumber, full width at half maximum (FWHM of these bands are dependent on quality of diamond layer which is dependent on the deposition conditions. The aim of the present work is to relate the features of diamond Raman spectra to the features of Raman spectra of non-diamond phase admixture and occurrence of other carbon structures in the obtained diamond thin films.

We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

Two types of independent anisotropic structures have been formed simultaneously in amorphoushydrogenated films by applying a femtosecond laser pulse to them, i.e., a structure with a period of several micrometers to several tens of micrometers and a structure with a period of several hundred nanometers. The formation mechanisms of these strictures are different, which allows us to orient them relative to each other in a desirable way. Both structures independently influence the optical properties of the modified films, which causes the diffraction of transmitted light and making the films polarization-sensitive. The conductivity of the modified films correlates with the mutual orientation of the anisotropic structures, whereas no interrelation between the photoconductivity and optical performance of the modified films has been observed.

Next generation experiments at the European laboratory of particle physics (CERN) require particle detector alternatives to actual silicon detectors. This thesis presents a novel detector technology, which is based on the deposition of a hydrogenatedamorphous silicon sensor on top of an integrated circuit. Performance and limitations of this technology have been assessed for the first time in this thesis in the context of particle detectors. Specific integrated circuits have been designed and the detector segmentation, the interface sensor-chip and the sensor leakage current have been studied in details. The signal induced by the track of an ionizing particle in the sensor has been characterized and results on the signal speed, amplitude and on the sensor resistance to radiation are presented. The results are promising regarding the use of this novel technology for radiation detection, though limitations have been shown for particle physics application. (author)

Full Text Available The two-component kinetic model employing “fast” and “slow” metastable defects for the annealing behaviors in pin-type hydrogenated-amorphous-silicon- (a-Si:H- based solar cells is simulated using a normalized fill factor. Reported annealing data on pin-type a-Si:H-based solar cells are revisited and fitted using the model to confirm its validity. It is verified that the two-component model is suitable for fitting the various experimental phenomena. In addition, the activation energy for annealing of the solar cells depends on the definition of the recovery time. From the thermally activated and high electric field annealing behaviors, the plausible microscopic mechanism on the defect removal process is discussed.

Growing evidence shows that several calcium carbonate biominerals form via an amorphous precursor phase. Such a biomineralization strategy could also be applicable for the biomimetic synthesis of novel functional materials. A crucial step in this process is the transformation of amorphous calcium carbonate (ACC) into calcite. However, controversy exists as to what is the actual mechanism of this transformation: Is it a solid-solid (solid state) or a dissolution/precipitation mechanism? Determining the transition mechanism is critical for example in interpreting the formation of oriented crystalline structures in biominerals (e.g., echinoderm spicles). We studied calcium carbonate precipitation and phase transitions according to the overall reaction Ca(OH)2 + CO2 = CaCO3+ H2O. Mineral phase transformations during this reaction were studied using transmission electron microscopy (TEM). Our TEM analysis showed that two different types of ACC are sequentially formed during this reaction. Type I ACC shows no well-defined short-range order, while Type II ACC shows a short-range order corresponding to calcite. Following e-beam irradiation, Type I ACC particles transform into randomly oriented CaO nanocrystals, while irradiation of Type II ACC leads to the formation of pseudomorphs made up of perfectly oriented aggregates of calcite nanocrystals. Moreover, calcite crystals formed in solution or in air (85 % relative humidity) after Type II ACC are also pseudomorphs made up of porous aggregates of preferentially oriented calcite nanocrystals. Our results give experimental evidence showing that the ACC to calcite transformation under relevant biomineralization conditions (low T and P), also applicable in the biomimetic synthesis of calcite, is a pseudomorphic dissolution-precipitation process. This mechanism involves the tightly interface-coupled dissolution of the precursor amorphous phase (with the crystalline phase protostructure) and concomitant deposition of the

In this paper we study the reaction of water and graphene under Extreme Ultraviolet (EUV) irradiation and in the presence of hydrogen. In this work, single layer graphene (SLG) on amorphous Si as an underlying substrate was dosed with water (0.75 ML) and exposed to EUV (λ = 13.5 nm, 92 eV) with

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphouscarbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH 3 as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about -80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH 3 is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp 2 sites dispersed in sp 3 skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films

We have shown that close to stoichiometry RF PECVD amorphous silicon carbon alloys deposited under silane starving plasma conditions exhibit a tendency towards c-Si C chemical order. Motivated by this trend, we further explore the effect of increasing RF power and H sub 2 dilution of the gaseous mixtures, aiming to obtain the amorphous counterpart of c-Si C by the RF-PECVD technique. Doping experiments were also performed on ordered material using phosphorus and nitrogen as donor impurities and boron and aluminum as acceptor ones. For nitrogen a doping efficiency close to device quality a-Si:H was obtained, the lower activation energy being 0,12 eV with room temperature dark conductivity of 2.10 sup - sup 3 (OMEGA.cm). Nitrogen doping efficiency was higher than phosphorous for all studied samples. For p-type doping, results indicate that, even though the attained conductivity values are not device levels, aluminum doping conducted to a promising shift in the Fermi level. Also, aluminum resulted a more efficie...

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC→anhydrous ACC ~ biogenic anhydrous ACC→vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO₂ sequestration.

Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. First, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce these interactions, we have selected two amorphoushydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a - SiC:H substrate can be beneficial in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a-SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a - C:H and a - SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modelling of hydrogen diffusion under irradiation has been also proposed. (author) 176 refs.

This work aims to define general criteria to allow theoretical and experimental design of new materials with high hydrogen content, with a view to their potential application as moderators in reactors at high temperatures and hydrogen storage materials. To this end we study the effects of Ni impurities on the properties of pure carbon (slabs as well as nanoparticles and gels) in order to analyze the thermodynamical characteristics, and improve the behavior of alloys for Ni-metal hydride rechargeable batteries. These elements are chosen because they have a wide range of solubility of hydrogen, which from the technological point of view makes them important candidates for the search for new materials. Our results show that this kind of carbon material could be used as support for hydrogen storage improving the screening charge density and the density of available states, as analyzed by the authors in previous works (author)

Full Text Available The spillover mechanism of molecular hydrogen on carbon nanotubes in the presence of catalytically active platinum clusters was critically and systematically investigated by using density-functional theory. Our simulation model includes a Pt4 cluster for the catalyst nanoparticle and curved and planar circumcoronene for two exemplary single-walled carbon nanotubes (CNT, the (10,10 CNT and one of large diameter, respectively. Our results show that the H2 molecule dissociates spontaneously on the Pt4 cluster. However, the dissociated H atoms have to overcome a barrier of more than 2 eV to migrate from the catalyst to the CNT, even if the Pt4 cluster is at full saturation with six adsorbed and dissociated hydrogen molecules. Previous investigations have shown that the mobility of hydrogen atoms on the CNT surface is hindered by a barrier. We find that instead the Pt4 catalyst may move along the outer surface of the CNT with activation energy of only 0.16 eV, and that this effect offers the possibility of full hydrogenation of the CNT. Thus, although we have not found a low-energy pathway to spillover onto the CNT, we suggest, based on our calculations and calculated data reported in the literature, that in the hydrogen-spillover process the observed saturation of the CNT at hydrogen background pressure occurs through mobile Pt nanoclusters, which move on the substrate more easily than the substrate-chemisorbed hydrogens, and deposit or reattach hydrogens in the process. Initial hydrogenation of the carbon substrate, however, is thermodynamically unfavoured, suggesting that defects should play a significant role.

Amorphouscarbon films of several thicknesses were prepared by graphite sputtering on crystalline silicon substrate. The samples were depth profiled with positron annihilation spectroscopy for open-volume measurements and characterized for their residual internal stress. It was found that after film growth the substrate presents vacancy-like defects decorated by oxygen in a layer extending in the substrate by several tens of nanometers beyond the film/Si interface. The width of the defected layer and the decoration of vacancy-like defects are directly and inversely proportional to the measured intensity of the residual stress, respectively. These findings indicate the existence of a relaxation mechanism of the stress in the films that involves deeply the substrate. The decorated vacancy-like defects are suggested to be bounded to dislocations induced in the substrate by the stress relaxation

Full Text Available Abstract The short-range order of individual fractal-like amorphouscarbon nanotips was investigated by means of energy-filtered electron diffraction in a transmission electron microscope (TEM. The nanostructures were grown in porous silicon substrates in situ within the TEM by the electron beam-induced deposition method. The structure factorS(k and the reduced radial distribution functionG(r were calculated. From these calculations a bond angle of 124° was obtained which suggests a distorted graphitic structure. Field emission was obtained from individual nanostructures using two micromanipulators with sub-nanometer positioning resolution. A theoretical three-stage model that accounts for the geometry of the nanostructures provides a value for the field enhancement factor close to the one obtained experimentally from the Fowler-Nordheim law.

The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

Single walled carbon nanotube networks (SWCNTNs) were coated by tetrahedral amorphouscarbon (ta-C) to improve the mechanical wear properties of the composite film. The ta-C deposition was performed by using pulsed filtered cathodic vacuum arc method resulting in the generation of C+ ions in the energy range of 40–60 eV which coalesce to form a ta-C film. The primary disadvantage of this process is a significant increase in the electrical resistance of the SWCNTN post coating. The increase in the SWCNTN resistance is attributed primarily to the intrinsic stress of the ta-C coating which affects the inter-bundle junction resistance between the SWCNTN bundles. E-beam evaporated carbon was deposited on the SWCNTNs prior to the ta-C deposition in order to protect the SWCNTN from the intrinsic stress of the ta-C film. The causes of changes in electrical resistance and the effect of evaporated carbon thickness on the changes in electrical resistance and mechanical wear properties have been studied.

The realization of manganese oxide anode materials for lithium-ion batteries is hindered by inferior cycle stability, rate capability, and high overpotential induced by the agglomeration of manganese metal grains, low conductivity of manganese oxide, and the high stress/strain in the crystalline manganese oxide structure during the repeated lithiation/delithiation process. To overcome these challenges, unique amorphous MnO{sub x}-C nanocomposite particles with interdispersed carbon are synthesized using aerosol spray pyrolysis. The carbon filled in the pores of amorphous MnO{sub x} blocks the penetration of liquid electrolyte to the inside of MnO{sub x}, thus reducing the formation of a solid electrolyte interphase and lowering the irreversible capacity. The high electronic and lithium-ion conductivity of carbon also enhances the rate capability. Moreover, the interdispersed carbon functions as a barrier structure to prevent manganese grain agglomeration. The amorphous structure of MnO{sub x} brings additional benefits by reducing the stress/strain of the conversion reaction, thus lowering lithiation/delithiation overpotential. As the result, the amorphous MnO{sub x}-C particles demonstrated the best performance as an anode material for lithium-ion batteries to date. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Carbon dioxide and the carbonates, the available natural C1 sources, can be easily hydrogenated into formic acid and formates in water; the rate of this reduction strongly depends on the pH of the solution. This reaction is catalysed by ruthenium(II) pre-catalyst complexes with a large variety of water-soluble phosphine ligands; high conversions and turnover numbers have been realised. Although ruthenium(II) is predominant in these reactions, the iron(II) - tris[(2-diphenylphosphino)-ethyl]phosphine (PP3) complex is also active, showing a new perspective to use abundant and inexpensive iron-based compounds in the CO2 reduction. In the catalytic hydrogenation cycles the in situ formed metal hydride complexes play a key role, their structures with several other intermediates have been proven by multinuclear NMR spectroscopy. In the other hand safe and convenient hydrogen storage and supply is the fundamental question for the further development of the hydrogen economy; and carbon dioxide has been recognised to be a viable H2 vector. Formic acid--containing 4.4 weight % of H2, that is 53 g hydrogen per litre--is suitable for H2 storage; we have shown that in aqueous solutions it can be selectively decomposed into CO-free (CO formic acid cleavage, in environmentally friendly propylene carbonate solution, opening the way to use cheap, non-noble metal based catalysts for this reaction, too.

A process for the hydrogenation of CO2 to methanol with a capacity of 10 kt/y methanol is designed in a systematic way. The challenge will be to obtain a process with a high net CO2 conversion. From initially four conceptual designs the most feasible is selected and designed in more detail. The

Chemical functionalization of carbon nanopore spaces has been shown to significantly increase the differential enthalpy of adsorption of hydrogen (ca. 9kJ/mol). This improved surface interaction corresponds to an increased density of the adsorbed film. Functionalized carbon samples have been produced through KOH activation, deposition of decaborane, and high temperature annealing. Hydrogen sorption measurements have shown significant improvements to stored film densities and binding energies. In this talk, a systematic study of the effect that boron concentration has on the samples' pore structures, binding energies, surface excess concentrations, and volumetric storage capacities is presented. Work supported by DOE-EERE, Award No. DE-FG36-08GO18142.

Titanium (Ti)-based materials have been used for dental/orthopedic implants due to their excellent biological compatibility, superior mechanical strength and high corrosion resistance. The osseointegration of Ti implants is related to their composition and surface treatment. Better biocompatibility and anti-bacterial performances of Ti implant are beneficial for the osseointegration and for avoiding the infection after implantation surgery. In this study, nanocomposite ZrCN/amorphouscarbon (a-C) coatings with different carbon contents were deposited on a bio-grade pure Ti implant material. A cathodic-arc evaporation system with plasma enhanced duct equipment was used for the deposition of ZrCN/a-C coatings. Reactive gas (N{sub 2}) and C{sub 2}H{sub 2} activated by the zirconium plasma in the evaporation process were used to deposit the ZrCN/a-C coatings. To verify the susceptibility of implant surface to bacterial adhesion, Actinobacillus actinomycetemcomitans (A. actinomycetemcomitans), one of the major pathogen frequently found in the dental implant-associated infections, was chosen for in vitro anti-bacterial analyses. In addition, the biocompatibility of human gingival fibroblast (HGF) cells on coatings was also evaluated by a cell proliferation assay. The results suggested that the ZrCN/a-C coatings with carbon content higher than 12.7 at.% can improve antibacterial performance with excellent HGF cell compatibility as well.

Titanium (Ti)-based materials have been used for dental/orthopedic implants due to their excellent biological compatibility, superior mechanical strength and high corrosion resistance. The osseointegration of Ti implants is related to their composition and surface treatment. Better biocompatibility and anti-bacterial performances of Ti implant are beneficial for the osseointegration and for avoiding the infection after implantation surgery. In this study, nanocomposite ZrCN/amorphouscarbon (a-C) coatings with different carbon contents were deposited on a bio-grade pure Ti implant material. A cathodic-arc evaporation system with plasma enhanced duct equipment was used for the deposition of ZrCN/a-C coatings. Reactive gas (N 2 ) and C 2 H 2 activated by the zirconium plasma in the evaporation process were used to deposit the ZrCN/a-C coatings. To verify the susceptibility of implant surface to bacterial adhesion, Actinobacillus actinomycetemcomitans (A. actinomycetemcomitans), one of the major pathogen frequently found in the dental implant-associated infections, was chosen for in vitro anti-bacterial analyses. In addition, the biocompatibility of human gingival fibroblast (HGF) cells on coatings was also evaluated by a cell proliferation assay. The results suggested that the ZrCN/a-C coatings with carbon content higher than 12.7 at.% can improve antibacterial performance with excellent HGF cell compatibility as well.

Magic angle spinning solid-state nuclear magnetic resonance spectroscopy techniques are applied to the elucidation of the local physical structure of an intermediate product in the plasma-enhanced chemical vapour deposition of thin-film amorphoushydrogenated boron carbide (B(x)C:H(y)) from an orthocarborane precursor. Experimental chemical shifts are compared with theoretical shift predictions from ab initio calculations of model molecular compounds to assign atomic chemical environments, while Lee-Goldburg cross-polarization and heteronuclear recoupling experiments are used to confirm atomic connectivities. A model for the B(x)C:H(y) intermediate is proposed wherein the solid is dominated by predominantly hydrogenated carborane icosahedra that are lightly cross-linked via nonhydrogenated intraicosahedral B atoms, either directly through B-B bonds or through extraicosahedral hydrocarbon chains. While there is no clear evidence for extraicosahedral B aside from boron oxides, ∼40% of the C is found to exist as extraicosahedral hydrocarbon species that are intimately bound within the icosahedral network rather than in segregated phases.

The interfaces in silicon thin film solar cells and silicon heterojunction solar cells are considered to be very important for the solar cell conversion efficiency. This work studies the interface properties of hydrogenatedamorphous silicon thin films deposited on crystalline silicon wafers after post-deposition hydrogen plasma treatment (HPT) or argon plasma treatment (APT). The investigation extends our previous study by examining the structural changes resulting from the post-deposition plasma treatment on silicon thin film solar cells. We analyzed the ellipsometry and infrared spectra of our samples to gain a deeper understanding of the fundamental plasma treatment effects. By using post-deposition APT and HPT, we were able to reduce the material stress and improve the structure of these layers. Our results show that APT yields a more compact material with fewer voids and less distinct localized tail states. We discuss the effect of APT and HPT on the most crucial interface in silicon heterojunction solar cells, the i-a-Si:H/c-Si interface. We propose to introduce APT as a post-deposition process step in the fabrication of silicon heterojunction solar cells.

Carbon based films can combine the properties of solid lubricating graphite structure and hard diamond crystal structure, i.e., high hardness, chemical inertness, high thermal conductivity and optical transparency without the crystalline structure of diamond. Issues of fundamental importance associated with nanocarbon coatings are reducing stress, improving adhesion and compatibility with substrates. In this work new nanocomposite coatings with improved toughness based in nanocrystalline phases of metals and ceramics embedded in amorphouscarbon matrix are being developed within the frame of a research project: nc-MeNxCy/a-C(Me) with Me = Mo, Si, Al, Ti, etc. Carbide forming metal/carbon (Me/C) composite films with Me = Mo, W or Ti possess appropriate properties to overcome the limitation of pure DLC films. These novel coating architectures will be adopted with the objective to decrease residual stress, improve adherence and fracture toughness, obtain low friction coefficient and high wear-resistance. Nanocomposite DLC's films were deposited by hybrid technique using a PVD-Physically Vapor Deposition (magnetron sputtering) and Plasma Enhanced Chemical Vapor Deposition (PECVD), by the use of CH4 gas. The parameters varied were: deposition time, substrate temperature (180 degrees C) and dopant (Si + Mo) of the amorphouscarbon matrix. All the depositions were made on silicon wafers and steel substrates precoated with a silicon inter-layer. The characterisation of the film's physico-mechanical properties will be presented in order to understand the influence of the deposition parameters and metal content used within the a-C matrix in the thin film properties. Film microstructure and film hybridization state was characterized by Raman Spectroscopy. In order to characterize morphology SEM and AFM will be used. Film composition was measured by Energy-Dispersive X-ray analysis (EDS) and by X-ray photoelectron spectroscopy (XPS). The contact angle for the produced DLC's on

Inelastic neutron scattering (INS) from adsorbed hydrogen offers a powerful tool to probe the local adsorption environment of storage material. We will show recently measured INS spectra of hydrogen adsorbed on four different carbon samples and discuss the interpretation of their spectral features, using previous theoretical calculations. Both rotational and vibrational transitions can be observed, along with free recoil scattering parallel to the adsorption plane. The spectra from carbon nanotubes and activated carbon are well explained by theory. However, the spectra from PVDC carbon is quite unusual. This material is based upon work supported in part by the Department of Energy under Award Nos. DE-FG02-07ER46411, DE-FG36-08GO18142, and DE-AC02-06CH11357.

In the present work it is studied the activated carbon of mineral origin for the sorption of hydrogen. The carbon decreased of particle size by means of the one alloyed mechanical. The time of mill was of 10 hours. The characterization one carries out by scanning electron microscopy and X-ray diffraction. The hydrogen sipped in the carbon material it was determined using the Thermal gravimetric method (TGA). The conditions of hydrogenation went at 10 atm of pressure and ambient temperature during 18 hours. They were also carried out absorption/desorption cycles of hydrogen in the same one system of thermal gravimetric analysis. The results showed percentages of sorption of 2% approximately in the cycles carried out in the system TGA and of 4.5% in weight of hydrogen at pressure of 10 atmospheres and ambient temperature during 18 hours. (Author)

Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applicatio...

Several novel proposals are examined for propellant production from carbon dioxide and monoxide and hydrogen. Potential uses were also examined of CO as a fuel or as a reducing agent in metal oxide processing as obtained or further reduced to carbon. Hydrogen can be reacted with CO to produce a wide variety of hydrocarbons, alcohols, and other organic compounds. Methanol, produced by Fischer-Tropsch chemistry may be useful as a fuel; it is easy to store and handle because it is a liquid at Mars temperatures. The reduction of CO2 to hydrocarbons such as methane or acetylene can be accomplished with hydrocarbons. Carbon monoxide and hydrogen require cryogenic temperatures for storage as liquid. Noncryogenic storage of hydrogen may be accomplished using hydrocarbons, inorganic hydrides, or metal hydrides. Noncryogenic storage of CO may be accomplished in the form of iron carbonyl (FE(CO)5) or other metal carbonyls. Low hydrogen content fuels such as acetylene (C2H2) may be effective propellants with low requirements for earth derived resources. The impact on manned Mars missions of alternative propellant production and utilization is discussed.

Complete text of publication follows: From an economic point of view, the use of hydrogen could revolutionize energy and transportation markets, what generates a great interest towards this fuel. This interest has led to the so-called 'hydrogen economy'. However, the main drawback for the use of hydrogen as transportation fuel or in power generation is the storage of this gas to reach a sufficiently high energy density, which could fit to the goals of the DOE hydrogen plan to automotive fuel cell systems i.e. 62 kg H 2 /m 3 ) [1]. A review of both experimental and theoretical studies published on the field of hydrogen storage on carbon materials (nano-tubes, nano-fibers and porous cartons) shows a large dispersion in hydrogen storage values. Although some values have exceeded by far the goals of the DOE [2], other authors assure that it is not feasible the use of carbonaceous materials as hydrogen storage systems [3]. The first objective of this presentation is to analyze some possible reasons of the large values dispersion. The discrepancy among the different theoretical studies can be due to non-realist models or to unsuitable approaches. High results dispersion and low reproducibility of experimental measurements are mostly consequence of experimental errors (as for example, the use of small amount of sample) and/or to the use of non-purified materials. In fact, the main disadvantage of the use of novel carbon materials, such as nano-tubes and nano-fibers, is the unavailability of large amounts of those materials with sufficient purity in order to get both feasible measurements in the laboratory, an their subsequent use in large scale. In addition to these possible reasons of errors, for a better understanding of the large results dispersion, the different mechanism of hydrogen storage, such as hydride formation, hydrogen transfer and hydrogen adsorption will be also reviewed in this presentation. Differently to nano-tubes and nano-fibers, activated carbons are

Carbon nanotubes (CNTs) are studied as a possible hydrogen storage medium for future energy needs. Typically, hydrogen is stored in the CNTs by exposure of the material to a high-pressure H 2 atmosphere at different temperatures. The maximum hydrogen concentrations stored following this method and measured using ion beam analysis do not exceed 1 wt.%. Introduction of defects by ion irradiation (i.e. implantation) prior to high-pressure H 2 treatment, offers an alternative method to activate H adsorption and enhance the chemisorption of hydrogen. This is a preliminary work where hydrogen was introduced into single-wall nanotubes and carbon films by low-energy (13.6 keV) hydrogen ion implantation. Elastic recoil detection was used to measure the quantity and depth distribution of hydrogen retained in the carbonaceous materials. Results show that there are substantial differences in the measured profiles between the CNT samples and the vitreous carbon. On another hand, only ∼43% of the implanted hydrogen in the CNTs is retained in the region where it should be located according to the SRIM simulations for a solid carbon sample

The new analytical method is based on the determination of the molar ratio carbonate - hydrogencarbonate using the measured concentration of hydrogen ions, the determination of the dissociation constant of carbonic acid for different values of ionic strength. The concentration of hydrogen ions was measured with a Metrohm 632 pH meter with the use of a combined glass electrode. The content of total carbonatecarbon was determined coulometrically and the uranium content was determined by extraction with tributyl phosphate and by spectrometry of the complex of uranyl ions with Arsenazo III. Model solutions were used for the experiments which contained a high concentration of sulfate ions, thiosulfate ions, uranium and various proportions of carbonate and hydrogencarbonate. The composition of the individual samples of the extraction solutions are tabulated. The calibration was made of the glass combined electrode at different ionic strength, the values determined of dissociation constants of carbonic acid for different ionic strength. The mathematical procedure is described for the calculation of molar concentrations of carbonate and hudrogen carbonate and the results are presented of the analysis of model solutions. (E.S.). 5 tabs., 1 fig., 5 refs

One-carbon and hydrogen metabolism of acidophilic verrucomicrobial methanotrophs Methane (CH4) is an essential molecule in the earth’s atmosphere and also very important for households and industry. Atmospheric methane contributes directly to the greenhouse effect. Global warming is a worldwide

We have developed a hybrid energy system for converting energy from renewable sources and its storage in the form of hydrogen. The storage uses activated carbon and the methodology was modelled mathematically and simulated in numerical software. The results show that storage compression is cheaper storage for liquefaction. [it

The Gordon-Kim electron gas model of molecular bonding is used to calculate correction factors for the Bragg rule for molecules of hydrogen and carbon. General rules for molecular mean excitation energies are obtained that agree to about 4% with experimental values.

Highlights: • This paper reports for the first time redistribution of hydrogen atoms in diamond like carbon thin films during ion implantation of low energy magnetic ions. • The results point towards new routes of controlling the composition and distribution of elements at the nanoscale within a base matrix without using any heat treatment methods. • Exploring these opportunities can lead to a new horizon of materials and device engineering needed for enabling advanced technologies and applications. - Abstract: Hydrogenated diamond-like carbon films produced by C{sub 3}H{sub 6} deposition at 5 kV and implanted at room temperature with 30 keV Co atoms to 12 at.% show not only a bimodal distribution of Co atoms but also a massive redistribution of hydrogen in the films. Resonant nuclear reaction analysis was used to measure the hydrogen depth profiles (15N-method). Depletion of hydrogen near the surface was measured to be as low as 7 at.% followed by hydrogen accumulation from 27 to 35 at.%. A model is proposed considering the thermal energy deposited by collision cascade for thermal insulators. In this model, sufficient energy is provided for dissociated hydrogen to diffuse out of the sample from the surface and diffuse into the sample towards the interface which is however limited by the range of the incoming Co ions. At a hydrogen concentration of ∼35 at.%, the concentration gradient of the mobile unbounded hydrogen atoms is neutralised effectively stopping diffusion towards the interface. The results point towards new routes of controlling the composition and distribution of elements at the nanoscale within a base matrix without using any heat treatment methods. Exploring these opportunities can lead to a new horizon of materials and device engineering needed for enabling advanced technologies and applications.

Composites with micro-sized magnetic particles dispersed in amorphouscarbon were fabricated conveniently and economically by carbonizing polyacrylonitrile (PAN) fibers mixed with micro-sized iron particles under different temperatures. The composites were characterized by X-ray diffraction (XRD) and scanning electric microscope (SEM). The electromagnetic (EM) properties were measured by a vector network analyzer in the frequency range of 2-18 GHz based on which analog computations of EM wave absorption properties were carried out. The influences of temperature on phase composition and EM wave absorption properties were also investigated, indicating that the composites had good electromagnetic absorption properties with both electrical loss and magnetic loss. Effective reflection loss (RL

Full Text Available Abstract We were deposited the as-deposited amorphouscarbon via a modified custom-made-CVD in the range of 350oC to 550oC at atmospheric pressure with constant of negative bias -40V and argon gas for 1 hour deposition. We used vaporized of palm oil as a carbon source into the chamber. It was observed above 90 of light were transmitted to the samples instead of sample 500oC 80. The as-deposited thin film grown on glass and p-type silicon we found uniform smooth dark grey colored and thickness in the range of 155 to 190nm. It was found thickness less than 170nm brought less significant impact to the reduction of transmission percentage. In relationship with structural image in FESEM the absorption coefficient was found high as the size of particles were big rough and agglomerated. The result showed the optical band gaps for 550oC to 350oC were 0.5eV 1.3eV 0.1eV 0.7eV and 1.4eV respectively. The optical band gaps of 400oC and 350oC were suitable for solar cell applications.

Solid polymer electrolytes (SPEs) have been proposed as substitutes for conventional non-aqueous electrolytes in various electrochemical devices. These promising materials may be of interest in various practical devices including batteries, sensors and electrochromic displays as they can offer high performance in terms of specific energy and specific power (batteries), safe operation, form flexibility in device arquitecture and low manufacturing costs. Many different host polymers have been characterized over the last 30 years, however a relatively un-explored strategy involves the use of interpenetrating blends incorporating two or more polymers. Electrolyte systems based on interpenetrating blends of known host polymers, poly(ethylene oxide) and poly(trimethylene carbonate), doped with lithium perchlorate, were prepared by co-dissolution in acetonitrile. This combination of polymer components results in the formation of a material that may be applicable in batteries and electrochromic devices. The results of characterization of polymer electrolyte systems based on interpenetrating blends of amorphous poly(ethylene oxide) and poly(trimethylene carbonate) host matrices, with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as guest salt, are described in this study. Electrolytes with compositions of n between 5 and 15 (where n represents the total number of cation-coordinating units per lithium ion) were obtained as flexible, transparent and free-standing films that were characterized by measurements of conductivity, cyclic voltammetry, differential scanning calorimetry and thermogravimetry.

This work reports on the induced diamond crystal amorphization by 4 MeV carbon ions implanted in the 〈1 0 0〉 oriented crystal and its determination by application of RBS/C and EBS/C techniques. The spectra from the implanted samples were recorded for 1.2, 1.5, 1.75 and 1.9 MeV protons. For the two latter ones the strong resonance of the nuclear elastic scattering 12C(p,p0)12C at 1.737 MeV was explored. The backscattering channeling spectra were successfully fitted and the ion beam induced crystal amorphization depth profile was determined using a phenomenological approach, which is based on the properly defined Gompertz type dechanneling functions for protons in the 〈1 0 0〉 diamond crystal channels and the introduction of the concept of ion beam amorphization, which is implemented through our newly developed computer code CSIM.

Among the energy storage technologies under development today, there is today an increasing interest towards the hydrogen-based ones. Hydrogen generation allows to store electricity, while its combustion can supply electrical, mechanical or heat energy. The French Atomic Energy Commission (CEA) started to work on hydrogen technologies at the end of the 1990's in order to reinforce its economical interest. The development of these technologies is one of the 34 French industrial programs presented in September 2013 by the French Minister of productive recovery. This paper aims at identifying the hydrogen stakes in a carbon-free energy mix and at highlighting the remaining technological challenges to be met before reaching an industrial development level

Full Text Available Methane gas (CH4 is the main inducer of the so called greenhouse gases effect. Recent scientific research aims to minimize the accumulation of this gas in the atmosphere and to develop processes capable of producing stable materials with added value. Thermal plasma technology is a promising alternative to these applications, since it allows obtaining H2 and solid carbon from CH4, without the parallel formation of byproducts such as CO2 and NOx. In this work, CH4 was degraded by thermal plasma in order to produce hydrogen (H2 and carbon black. The degradation efficiency of CH4, selectivity for H2 production as well as the characterization of carbon black were studied. The best results were obtained in the CH4 flow rate of 5 L min-1 the degradation percentage and the selectivity for H2 production reached 98.8 % and 48.4 %, respectively. At flow rates of less than 5 L min-1 the selectivity for H2 production increases and reaches 91.9 %. The carbon black has obtained amorphous with hydrophobic characteristics and can be marketed to be used in composite material, and can also be activated chemically and/or physically and used as adsorbent material.

We used Grand canonical Monte Carlo simulation to model the hydrogen storage in the primitive, gyroid, diamond, and quasi-periodic icosahedral nanoporous carbon materials and in carbon nanotubes. We found that none of the investigated nanoporous carbon materials satisfy the US Department of Energy goal of volumetric density and mass storage for automotive application (6 wt% and 45 kg H(2) m(-3)) at considered storage condition. Our calculations indicate that quasi-periodic icosahedral nanoporous carbon material can reach the 6 wt% at 3.8 MPa and 77 K, but the volumetric density does not exceed 24 kg H(2) m(-3). The bundle of single-walled carbon nanotubes can store only up to 4.5 wt%, but with high volumetric density of 42 kg H(2) m(-3). All investigated nanoporous carbon materials are not effective against compression above 20 MPa at 77 K because the adsorbed density approaches the density of the bulk fluid. It follows from this work that geometry of carbon surfaces can enhance the storage capacity only to a limited extent. Only a combination of the most effective structure with appropriate additives (metals) can provide an efficient storage medium for hydrogen in the quest for a source of "clean" energy.

Mineral formation by nonclassical processes is widespread with many pathways that include aggregation of nanoparticles, oriented attachment of fully formed crystals, and sequential nucleation/transformation of amorphous phases (De Yoreo et al., 2015, Science). Field observations indicate amorphous calcium carbonate (ACC) can be the initial precipitate when local conditions promote high supersaturations for short time periods. Examples include microbial mats, marine porewaters that undergo pulses of increased alkalinity, closed basin lakes, and sabkhas. The crystalline products exhibit diverse morphologies and complex elemental and isotopic signatures. This study quantifies relationships between solution composition and the crystalline polymorphs that transform from ACC (Blue et al., GCA, 2017). Our experimental design synthesized ACC under controlled conditions for a suite of compositions by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within output suspensions under stirred or quiescent mixing while characterizing the polymorph and composition of evolving solutions and solids. We find that ACC transforms to crystalline polymorphs with a systematic relationship to solution composition to give a quantitative framework based upon solution aMg2+/aCa2+ and aCO32-/aCa2+. We also measure a polymorph-specific evolution of pH and Mg/Ca during the transformation that indicates the initial polymorph to form. Pathway is further modulated by stirring versus quiescent conditions. The findings reconcile discrepancies among previous studies of ACC to crystalline products and supports claims that monohydrocalcite may be an overlooked, transient phase during formation of some aragonite and calcite deposits. Organic additives and extreme pH are not required to tune composition and polymorph. Insights from this study reiterate the need to revisit long-standing dogmas regarding controls on CaCO3 polymorph selection. Classical models

More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphouscarbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert

Hydrogen produced using the steam reforming process contains sulfur and carbon monoxide that are harmful to the Pt catalyst in proton-exchange-membrane fuel cells (PEMFCs). However, CO-free hydrogen can be generated from the hydrolysis of either Al in strongly alkaline water or Mg in neutral water with chlorides such as sea water. The hydrogen generation rate from the hydrolysis of Mg is extremely slow and linearly proportional to the corrosion rate of Mg in chloride water. In this work, we fabricated a carbon nanotube (CNT)--reinforced Mg--matrix composite by Spark Plasma Sintering as a fast hydrogen generation source for a PEMFC. The CNTs distributed in the Mg matrix act as numerous local cathodes, and hence cause severe galvanic corrosion between the Mg-matrix anode and CNT-cathode in NaCl solution. It was found that the hydrogen generation rate from the hydrolysis of the 5 vol.% CNT/Mg composite is 3300 times faster than that of the Mg without CNTs due primarily to the galvanic corrosion effect.

This paper presents a review of hydrogen and helium recycling phenomena in tokamaks with limiters and walls largely made out of carbon (graphite, a-C:H layers). The key points of interest are the plasma fuelling efficiency, the wall pumping phenomena as observed in JET, TFTR, TEXTOR and other machines under various fuelling schemes (gas, neutral beams, pellets), the release of hydrogen/helium from material surfaces during and after plasma discharges and the long term retention (total particle inventory) of hydrogen in graphite or carbonised structures in tokamaks. The effect of a combined hydrogen/helium plasma on recycling is also discussed. It is shown that only part of the above phenomena can be understood in terms of processes between hydrogen/helium and carbon as known from simulation experiments (ion beams, gas discharge facilities) and that others (in particular the JET wall pumping phenomenon) have still to be explained. Possible mechanisms are outlined and discussed by means of global models. (orig.)

Amorphoushydrogenated silicon films different in thickness (600 - 2400 nm) were deposited by plasma enhanced chemical vapour deposition on Corning glass substrates at 250 C using silan 10% / argon 90% gas mixture. The samples were consequently isothermally heated in a high temperature vacuum chamber at 0.1 Pa and at temperatures from 580 to 620 C. In order to evaluate structural and optical properties of the films X-ray diffraction analysis, Raman spectrometry and optical spectrophotometry were used. Crystalline state (amorphous or microcrystalline), optical band gaps, refractive indices, extinction coefficients, absorption coefficients were determined. X-ray diffraction analysis indicated that originally deposited films were amorphous with different degree of homogeneity depending on the film thickness. After the heat treatment the films became polycrystalline with crystallite sizes 40-50 nm without particular dependence on the recrystallization process used. Raman spectrometry confirmed the results obtained from X-ray diffraction and furthermore revealed the residual amorphous phase 20-25% in volume. Optical spectrophotometry has shown that the values of refractive indices of thermally treated films approach the mono-crystalline silicon refractive index. Extinction coefficients of the thermally treated films are slightly higher than those for monocrystalline silicon. Absorption coefficients for thermally treated films reached quite high values near the absorption edge of the original amorphous material, which can be advantageous for tandem solar cell technologies. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Successful conversion of renewable energy to useful chemicals requires efficient devices that can electrocatalyze or photocatalyze redox reactions, e.g., overall water splitting. Excellent electrocatalysts for the hydrogen evolution reaction (HER), such as Pt, can also cause other side-reactions, including the water-forming back-reaction from H2 and O2 products. A Cr-based amorphous layer coated on catalysts can work as a successful surface modifier that avoids the back-reaction, but its capabilities and limitations toward other species have not been studied. Herein, we investigated the Cr-based layer on Pt from perspectives of both electrocatalysis and photocatalysis using redox-active molecules/ions (O2, ferricyanide, IO3–, S2O82–, H2O2, and CO gas). Our systematic study revealed that utilization of the Cr-based layer realized an exclusive cathodic reaction only to HER, even in the presence of the aforementioned reactive species, suggesting that Cr-based layers work as membranes, as well as corrosion and poison inhibition layers. However, the Cr-based layer experienced self-oxidation and dissolved into the aqueous phase when a strong oxidizing agent or low pH was present. Presented herein are fundamental and critical aspects of the Cr-based modifier, which is essential for the successful and practical development of solar fuel production systems.

A scattering matrix (S-matrix) analysis method was developed for evaluating hydrogenatedamorphous silicon (a-Si:H)-based thin film solar cells. In this approach, light wave vectors A and B represent the incoming and outgoing behaviors of the incident solar light, respectively, in terms of coherent wave and incoherent intensity components. The S-matrix determines the relation between A and B according to optical effects such as reflection and transmission, as described by the Fresnel equations, scattering at the boundary surfaces, or scattering within the propagation medium, as described by the Beer-Lambert law and the change in the phase of the propagating light wave. This matrix can be used to evaluate the behavior of angle-incident coherent and incoherent light simultaneously, and takes into account not only the light scattering process at material boundaries (haze effects) but also nonlinear optical processes within the material. The optical parameters in the S-matrix were determined by modeling both a 2%-gallium-doped zinc oxide transparent conducting oxide and germanium-compounded a-Si:H (a-SiGe:H). Using the S-matrix equations, the photocurrent for an a-Si:H/a-SiGe:H tandem cell and the optical loss in semitransparent a-Si:H solar cells for use in building-integrated photovoltaic applications were analyzed. The developed S-matrix method can also be used as a general analysis tool for various thin film solar cells.

The study first uses numerical simulations of hexagonal triangle and sphere arrays to optimize the performance of hydrogenatedamorphous silicon (a-Si:H) photovoltaic devices. The simulations indicated the potential for a sphere array to provide optical enhancement (OE) up to 7.4% compared to a standard cell using a nanosphere radius of 250 nm and silver film thickness of 50 nm. Next a detailed series of a-Si:H cells were fabricated and tested for quantum efficiency and characteristic and current-voltage (I-V) profiles using a solar simulator. Triangle and sphere array based cells, as well as the uncoated reference cells are analyzed and the results find that the simulation does not precisely predict the observed enhancement, but it forecasts a trend and can be used to guide fabrication. In general, the measured OE follows the simulated trend: (1) for triangular arrays no enhancement is observed and as the silver thickness increases the more degradation of the cell; (2) for annealed arrays both measured and simulated OE occur with the thinner silver thickness. Measured efficiency enhancement reached 20.2% and 10.9% for nanosphere diameter D = 500 nm, silver thicknesses h = 50 nm and 25 nm, respectively. These values, which surpass simulation results, indicate that this method is worth additional investigation.

Dielectric nanosphere arrays are considered as promising light-trapping designs with the capability of transforming the freely propagated sunlight into guided modes. This kinds of designs are especially beneficial to the ultrathin hydrogenatedamorphous silicon (a-Si:H) solar cells due to the advantages of using lossless material and easily scalable assembly. In this paper, we demonstrate numerically that the front-sided integration of high-index subwavelength titanium dioxide (TiO2) nanosphere arrays can significantly enhance the light absorption in 100 nm-thick a-Si:H thin films and thus the power conversion efficiencies (PCEs) of related solar cells. The main reason behind is firmly attributed to the strong scattering effect excited by TiO2 nanospheres in the whole waveband, which contributes to coupling the light into a-Si:H layer via two typical ways: 1) in the short-waveband, the forward scattering of TiO2 nanospheres excite the Mie resonance, which focuses the light into the surface of the a-Si:H layer and thus provides a leaky channel; 2) in the long-waveband, the transverse waveguided modes caused by powerful scattering effectively couple the light into almost the whole active layer. Moreover, the finite-element simulations demonstrate that photocurrent density (Jph) can be up to 15.01 mA/cm(2), which is 48.76% higher than that of flat system.

Full Text Available Nanomaterials, such as Graphene, h-BN nanoparticles and MoS2 nanotubes, have shown their ability in improving the tribological performance of amorphouscarbon (a-C coatings. In the current study, the effectiveness of ZrO2 nanoparticles (ZrO2-NPs in lubricating the self-mated nonhydrogenated a-C contacts was investigated in boundary lubrication regime. The results showed that 13% less friction and 50% less wear compared to the base oil were achieved by employing ZrO2-NPs in the base oil in self-mated a-C contacts. Via analyzing the ZrO2-NPs and the worn a-C surface after tests, it was found that the improved lubrication by ZrO2-NPs was based on “polishing effects”, which is a new phenomenon observed between a-C and nanoparticles. Under the “polishing effect”, micro-plateaus with extremely smooth surface and uniform height were produced on the analyzed a-C surface. The resulting topography of the a-C coating is suitable for ZrO2-NPs to act as nano-bearings between rubbing surfaces. Especially, the ZrO2-NPs exhibited excellent mechanical and chemical stability, even under the severe service condition, suggesting that the combination of nonhydrogenated a-C coating with ZrO2-NPs is an effective, long lasting and environment-friendly lubrication solution.

This work reports on a tribological study of magnetron-sputtered silicon-containing amorphouscarbon thin films vs. their alumina counterparts. Temperature cycling during ball-on-disk tests in humid air revealed a decrease in the coefficient of friction from 0.3 to <0.02 beyond 240 ± 15 °C. Systematic variation of the environment confirmed oxygen to be responsible for the low friction. X-ray photoelectron spectroscopy of the wear tracks indicates oxidation of Si-C bonds and formation of Si-O-C bonds, followed by further oxidation to SiO 2 above 450 °C. Ab initio molecular dynamics simulations of gas interactions with the a-C surface revealed dissociation of O 2 and the formation of oxides. Additional density functional theory calculations of Si incorporation into a graphene layer, resembling the surface of the film, showed preferential attraction of gaseous species (H, O, -OH, H 2 O), to Si-sites as compared to C-sites. Hence, the temperature- and atmosphere-induced changes in friction coefficient can be understood based on correlative X-ray photoelectron spectroscopy and ab initio data: the formation of Si-O-C bonds stemming from a reaction of the as-deposited coating with atmosphere in the tribological contact is observed by theory and experiment

Electrochemistry and nucleation mechanism of induced co-deposition of cobalt, tungsten and phosphorus from a citrate bath was investigated using voltammetry and chronoamperometry techniques. It was found that the induced co-deposition of the species occurred under diffusion control and followed instantaneous nucleation mechanism. Co-W-P coatings were electrodeposited potentiostatically on plain carbon steels from a citrate bath containing CoSO 4 , Na 2 WO 4 and NaH 2 PO 2 . X-ray diffraction studies of the coatings revealed that the as-deposited Co 81 W 10 P 9 coatings had amorphous structure. The formation of some stoichiometric compounds like Co 3 W, Co 2 P and WP 2 , however, was observed upon annealing at 600 deg. C. The hardness of the Co-W-P coatings increased with annealing temperature which was possibly due to the formation of these inter-elemental compounds. The corrosion resistance of the Co-W-P coatings increased with increase in annealing temperature which might also be due to the formation of the stoichiometric compounds at elevated temperatures. A comparison between coating characteristics of Co-W-P and chromium showed that the Co-W-P coatings exhibited nobler corrosion potential than chromium coatings

A parametric study has been performed of amorphous tetrahedral carbon (a-tC) films produced by ion-assisted pulsed laser deposition (IAPLD). The ion voltage, current density, and feed gas composition (nitrogen in argon) have been varied. The resultant films were characterized by thickness, residual stress, Raman spectroscopy, and electrical resistivity. The Raman spectra have been fit to two gaussian peaks, the so called graphitic (G) peak and the disorder (D) peak. It has been found that the magnitude of the D peak and the residual compressive stress are inversely correlated. At low beam voltages and currents, the magnitude of the D peak is low, increasing as the ion beam voltage and current are raised. The ion beam voltage has the most dramatic effect on the magnitude of the D peak. At low voltages (200-500 V) the magnitude of the D peak is greater for ion beams with high percentages of nitrogen possibly indicative of C-N bonding in the films. At higher voltages (500-1500 V) the D peak intensity is less sensitive to the nitrogen content of the beam.

Amorphouscarbon (a-C) solar cells were successfully prepared using a novel and self-designed aerosol-assisted chemical vapor deposition (AACVD) method using camphor oil as a precursor. The fabricated solar cell with the configuration of Au/p-C/n-Si/Au achieved an efficiency of 0.008% with a fill factor of 0.15 for the device deposited at 0.5 h. The current-voltage (I-V) graph emphasized on the linear graph (ohmic) for the a-C thin films, whereas for the p-n device structure, a rectifying curve was obtained. The rectifying curves signify the heterojunction between the p-type a-C film and the n-Si substrate and designate the generation of electron-hole pair of the samples under illumination. Photoresponse characteristics of the deposited a-C was highlighted when being illuminated (AM 1.5 illumination: 100 mW/cm2, 25 °C). Transmittance spectrum exhibit a large transmittance value (>85%) and absorption coefficient value of 103-104 cm-1 at the visible range of 390 to 790 nm. The atomization of a liquid precursor solution into fine sub-micrometre-sized aerosol droplets in AACVD induced the smooth surface of a-C films. To the best of our knowledge, fabrication of a-C solar cell using this AACVD method has not yet been reported.

The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

For the fabrication of a multilevel resist (MLR) based on a very thin, physical-vapor-deposited (PVD) amorphouscarbon (a-C) layer, the etching characteristics of the PVD a-C layer with a SiO x hard mask were investigated in a dual-frequency superimposed capacitively coupled plasma etcher by varying the following process parameters in O 2 /N 2 /Ar plasmas: high-frequency/low-frequency combination (f HF /f LF ), HF/LF power ratio (P HF /P LF ), and O 2 and N 2 flow rates. The very thin nature of the a-C layer helps to keep the aspect ratio of the etched features low. The etch rate of the PVD a-C layer increased with decreasing f HF /f LF combination and increasing P LF and was initially increased but then decreased with increasing N 2 flow rate in O 2 /N 2 /Ar plasmas. The application of a 30 nm PVD a-C layer in the MLR structure of ArF PR/BARC/SiO x /PVD a-C/TEOS oxide supported the possibility of using a very thin PVD a-C layer as an etch-mask layer for the TEOS-oxide layer

Electrochemical deposition technique was used to fabricate titanium doped amorphouscarbon (Ti doped a:C) Al/Ti-a:C/p-Si/Al photodiode. The effects of illumination on the current-voltage (I-V) characteristics of the Al/a:C/p-Si/Al doped Ti diode for optoelectronic applications were investigated. The reverse current of the diode increased with the increasing illumination intensities when the bias voltage was applied. By using the forward bias I-V characteristics, the ideality factor (n) and barrier height (Φb) of Al/Ti-a:C/p-Si photodiode structure was found as 1,84 and 0,50 eV, respectively. In addition, the capacitance-voltage (C-V) and conductance-voltage (G-V) measurements of the diode were studied in the frequency range of 100 kHz-600 kHz. The measured values of the capacitance decreased with the increasing frequency. The photoelectrical properties of Al/Ti-a:C/p-Si/Al device indicates that the photodiode investigated in this paper has great potential to be used in optoelectronic device applications and in industry.

Amorphouscarbon nanotubes (a-CNTs) were synthesized by solid state reaction. The as prepared a-CNTs were characterized by X-ray diffraction, field emission scanning and high resolution transmission electron microscope and Raman spectroscopy. As-synthesized a-CNTs were used for, the first time, for removing different organic dyes from water. The dyes mainly include Rhodamine B and Methyl Orange and systematic batch mode studies of a-CNTs assisted adsorption have been executed in detail. The removing efficiency of a-CNTs has also been investigated for various sorption parameters like contact time, dosage, pH, initial dye concentration, contact time etc. It is seen that a-CNTs can be material of potential for removal of dyes. In case of Rhodamine B, the maximum time for removal was 45 min whereas for Methyl orange rapid removal was plausible in about 30 min even in ambient condition. The experimental data have been well correlated with classical Langmuir-Freundlich and Temkin adsorption models.

Amorphouscarbon nanotubes (a-CNTs) manganese di oxide (MnO2)-poly pyrrole (PPy) ternary nanocomposites have been synthesized by a simple chemical route. The as prepared samples have been characterized with different characterization tools that include field emission scanning and high resolution transmission electron microscopy, Raman, Fourier transformed infrared as well as UV-Vis spectroscopy. The electrochemical performance of all the as prepared pure and hybrid samples have been studied in detail. It has been seen that the ternary hybrid shows efficient electrochemical performance with high value of specific capacitance with good stability even up to 2000 cycles. The superior performance of the hybrid samples can be attributed to the strong synergistic effect between the components resulting electron shuttling along PPy main chains and inter-chain raising built-in continuous conductive network. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications. These studies can well speculate the existence of another supercapacitor hybrid for the use in environment friendly electrode and thus a pollution free nature.

Short-pulse-laser-induced damage and ablation of thin films of amorphous, diamond-like carbon have been investigated. Material removal and damage are caused by fracture of the film and ejection of large fragments. The fragments exhibit a delayed, intense and broadband emission of microsecond duration. Both fracture and emission are attributed to the laser-initiated relaxation of the high internal stresses of the pulse laser deposition-grown films.

The field emission capability of the carbon nanotubes (CNTs) has been improved by hydrogen plasma treatment, and the enhanced emission mechanism has been studied systematically using Fourier-transform infrared spectroscopy, Raman, and transmission electron microscopy. The hydrogen concentration in the samples increases with increasing plasma treatment duration. A C δ- -H δ+ dipole layer may form on CNTs' surface and a high density of defects results from the plasma treatment, which is likely to make the external surface of CNTs more active to emit electrons after treatment. In addition, the sharp edge of CNTs' top, after removal of the catalyst particles, may increase the local electronic field more effectively. The present study suggests that hydrogen plasma treatment is a useful method for improving the field electron emission property of CNTs

Carbon-oxygen (CH···O) hydrogen bonding represents an unusual category of molecular interactions first documented in biological structures over 4 decades ago. Although CH···O hydrogen bonding has remained generally underappreciated in the biochemical literature, studies over the last 15 years have begun to yield direct evidence of these interactions in biological systems. In this minireview, we provide a historical context of biological CH···O hydrogen bonding and summarize some major advancements from experimental studies over the past several years that have elucidated the importance, prevalence, and functions of these interactions. In particular, we examine the impact of CH···O bonds on protein and nucleic acid structure, molecular recognition, and enzyme catalysis and conclude by exploring overarching themes and unresolved questions regarding unconventional interactions in biomolecular structure. PMID:23048026

Coaxial mesoporous MnO2/amorphous-carbon nanotubes have been synthesized via a facile and cost-effective strategy at room temperature. The coaxial double nanotubes of inner (outer) MnO2 and outer (inner) amorphouscarbon can be obtained via fine tuning the preparative factors (e.g., deposition order and processing temperature). Furthermore, the electrochemical properties of the coaxial nanotubes were evaluated by cycle voltammetric (CV) and galvanostatic charge-discharge (GC) measurements. The as-prepared coaxial double nanotubes of outer MnO2 and inner amorphouscarbon exhibit the optimized pseudocapacitance performance (362 F g-1) with good cycling stability, and ideal rate capability owning to the unique nanostructures. When assembled into two-electrode asymmetric supercapacitor, an energy density of 22.56 W h kg-1 at a power density of 224.9 W kg-1 is obtained. These findings provide a new and facile approach to fabricate high-performance electrode for supercapacitors.

The use of helium nano droplets as a matrix to investigate different atomic and molecular samples is a well established experimental technique. The unique properties of helium allow for different analytical methods and at the same time provide a stable ambient temperature. Cluster growth inside helium nano droplets can be accomplished by repeatedly doping the droplets with sample particles in a controlled environment. The experimental work represented in this thesis was performed using helium nano droplets to create clusters of fullerenes like C 60 and C 70 . The adsorption properties of these fullerene clusters regarding hydrogen and hydrogen rich molecules have been subject to investigation. The observed results suggest that curved carbon nano surfaces offer higher storage densities than planar graphite surfaces. The use of C 60 as a model carbon nano structure provides a well understood molecule for testing and evaluating computational methods to calculate surface properties of various carbon nano materials. The cost effective storage of hydrogen for mobile applications plays a key role in the development of alternatives to fossil fuels. For that reason, the application of carbon nano materials to store hydrogen by adsorption has attracted much scientific attention lately. The insights gained in the presented thesis contribute to the collective efforts and deliver more refined tools to estimate the adsorption properties of future carbon nano materials. In addition to the aforementioned, a time-of-flight mass spectrometer for educational purpose has been designed and constructed in the framework of my PhD thesis. The instrument is successfully used in various lab courses and information on the setup can be found in the Appendix of this work. (author) [de

We examined the electronic and mechanical properties of hydrogen functionalized carbon nanotubes. The functionalization pattern covers two extreme groups. One group has randomly selected functionalization sites including one to twenty percent of the carbon atoms. The other group has regularly patterned functional sites parallel to the tube axis. Metallic, small-gap semiconducting and large-gap semiconducting carbon nanotubes are studied. The results reveal that the electronic properties of the tubes are very sensitive to the degree of functionalization, with even one percent functionalization being enough to render metallic tubes semiconducting. On the other hand, the mechanical properties, like tensile modulus, are much less sensitive to functionalization. For carbon nanotubes functionalized with specific patterns, the electric properties depends strongly on the nature of the functionalization pattern.

Research undertaken has added to the understanding of several critical areas, by providing both negative answers (and therefore eliminating expensive further studies of unfeasible paths) and positive feasible options for storage. Theoretical evaluation of the early hypothesis of storage on pure carbon single wall nanotubes (SWNT) has been scrutinized with the use of comprehensive computational methods (and experimental tests by the Center partners), and demonstrated that the fundamentally weak binding energy of hydrogen is not sufficiently enhanced by the SWNT curvature or even defects, which renders carbon nanotubes not practical media. More promising direction taken was towards 3-dimensional architectures of high porosity where concurrent attraction of H2 molecule to surrounding walls of nano-scale cavities can double or even triple the binding energy and therefore make hydrogen storage feasible even at ambient or somewhat lower temperatures. An efficient computational tool has been developed for the rapid capacity assessment combining (i) carbon-foam structure generation, (ii) accurate empirical force fields, with quantum corrections for the lightweight H2, and (iii) grand canonical Monte Carlo simulation. This made it possible to suggest optimal designs for carbon nanofoams, obtainable via welding techniques from SWNT or by growth on template-zeolites. As a precursor for 3D-foams, we have investigated experimentally the synthesis of VANTA (Vertically Aligned NanoTube Arrays). This can be used for producing nano-foams. On the other hand, fluorination of VANTA did not show promising increase of hydrogen sorption in several tests and may require further investigation and improvements. Another significant result of this project was in developing a fundamental understanding of the elements of hydrogen spillover mechanisms. The benefit of developed models is the ability to foresee possible directions for further improvement of the spillover mechanism.

The purpose of this study is to understand the annealing behavior of hydrogen isotopes in carbon based materials. Also, the density of the material and structural changes after thermal treatment and ion irradiation are examined. The study of hydrogen diffusion in diamondlike carbon films revealed an activation energy of 2.0 eV, while the deuterium diffusion, due to better measuring sensitivity, is found to be concentration dependent with the effective diffusion coefficient becoming smaller with decreasing deuterium concentration. To explain the experimentally observed profiles, a model according to which atomic deuterium diffuses and deuterium in clusters is immobile is developed. The concentration of immobile D was assumed to be an analytical function of the total D concentration. To describe the annealing behavior of D incorporated in diamondlike carbon films during the deposition process, a model taking into account diffusion of free D and thermal detrapping and trapping of D was developed. The difference in the analysis explains the disagreement of activation energy (1.5 ± 0.2 eV) with the value of 2,9± 0.1 eV obtained for D implanted samples earlier. The same model was applied to describe the experimental profiles in Si doped diamondlike carbon films. Si affects the retention of D in diamondlike carbon films. The amount of D depends on Si content in the co-deposited but not implanted samples. Besides, Si incorporation into carbon coating decreases to some extent the graphitization of the films and leads to formation of a structure which is stable under thermal treatment and ion irradiation. Hydrogen migration in the hydrogen and methane co-deposited films was also studied. In samples produced in methane atmosphere and annealed at different temperatures, the hydrogen concentration level decreases in the bulk, with more pronounced release at the surface region. In the case of coatings deposited by a methane ion beam, the H level also decreases with increasing

Studies on the creation of nanosized membrane reactors (NMRs) of a new generation with accumulated hydrogen and a regulated volume of reaction zone were continued at the next stage. Hydrogenation was performed in the pores of ceramic membranes with hydrogen preliminarily adsorbed in mono- and multilayered orientated carbon nanotubes with graphene walls (OCNTGs)—a new hybrid carbon nanostructure formed on the inner pore surface. Quantitative determination of hydrogen adsorption in OCNTGs was performed using TRUMEM ultrafiltration membranes with D av = 50 and 90 nm and showed that hydrogen adsorption was up to ˜1.5% of the mass of OCNTG. The instrumentation and procedure for noncatalytic hydrogenation of decene-1 at 250-350°C using hydrogen accumulated and stored in OCNTG were developed. The conversion of decene-1 into decane was ˜0.2-1.8% at hydrogenation temperatures of 250 and 350°C, respectively. The rate constants and activation energy of hydrogenation were determined. The latter was found to be 94.5 kJ/mol, which is much smaller than the values typical for noncatalytic hydrogenations and very close to the values characteristic for catalytic reactions. The quantitative distribution of the reacting compounds in each pore regarded as a nanosized membrane reactor was determined. The activity of hydrogen adsorbed in a 2D carbon nanostructure was evaluated. Possible mechanisms of noncatalytic hydrogenation were discussed.

The development of efficient photocatalytic material for converting solar energy to hydrogen energy as viable alternatives to fossil-fuel technologies is expected to revolutionize energy shortage and environment issues. However, to date, the low quantum yield for solar hydrogen production over photocatalysts has hindered advances in the practical applications of photocatalysis. Here, we show that a carbon nitride intercalation compound (CNIC) synthesized by a simple molten salt route is an efficient polymer photocatalyst with a high quantum yield. We found that coordinating the alkali metals into the C-N plane of carbon nitride will induce the un-uniform spatial charge distribution. The electrons are confined in the intercalated region while the holes are in the far intercalated region, which promoted efficient separation of photogenerated carriers. The donor-type alkali metal ions coordinating into the nitrogen pots of carbon nitrides increase the free carrier concentration and lead to the formation of novel nonradiative paths. This should favor improved transport of the photogenerated electron and hole and decrease the electron-hole recombination rate. As a result, the CNIC exhibits a quantum yield as high as 21.2% under 420 nm light irradiation for solar hydrogen production. Such high quantum yield opens up new opportunities for using cheap semiconducting polymers as energy transducers.

Novel carbon-free integrated system of hydrogen production and storage from low rank coal is proposed and evaluated. To measure the optimum energy efficiency, two different systems employing different chemical looping technologies are modeled. The first integrated system consists of coal drying, gasification, syngas chemical looping, and hydrogenation. On the other hand, the second system combines coal drying, coal direct chemical looping, and hydrogenation. In addition, in order to cover the consumed electricity and recover the energy, combined cycle is adopted as addition module for power generation. The objective of the study is to find the best system having the highest performance in terms of total energy efficiency, including hydrogen production efficiency and power generation efficiency. To achieve a thorough energy/heat circulation throughout each module and the whole integrated system, enhanced process integration technology is employed. It basically incorporates two core basic technologies: exergy recovery and process integration. Several operating parameters including target moisture content in drying module, operating pressure in chemical looping module, are observed in terms of their influence to energy efficiency. From process modeling and calculation, two integrated systems can realize high total energy efficiency, higher than 60%. However, the system employing coal direct chemical looping represents higher energy efficiency, including hydrogen production and power generation, which is about 83%. In addition, optimum target moisture content in drying and operating pressure in chemical looping also have been defined.

We present results from a structural study of the transformation of freeze dried amorphous calcium carbonate, ACC, in crystalline material using pair distribution function analysis, PDF analysis, of X-ray powder diffraction data, XPD data. PDF analysis allows for the analysis of local order of structural subunit in the range between molecular unit (1. and 2. coordination sphere) and long range periodicity as in crystalline materials. ACC was precipitated from aqueous solutions at 298 K and 278 K using different amounts of Mg cations as stabilizer. The samples were immediately separated from the solution and freeze dried. For the transformation study, the samples were heated and analysed using XPD until they were crystallized. The radial distribution obtained from the XPD data were compared to simulated radial distributions of the calcium carbonate polymorphs and their hydrated phases. An ACC precipitated from a solution with Ca:Mg:CO3 = 1:5:4 at 298 K (ration in mmol, pH = 8.2) and freeze dried right after isolation from the solution revealed a close resemblance with ikaite in its local order. Another ACC with Ca:Mg:CO3 = 1:10:1.4 (T = 298, pH = 8.7) showed distinctly different local order resembling monohydrocalcite. Both ACC, however, still had considerable amounts of water dominating the Ca-coordination sphere. During the transformation to calcite, the structural changes in the sample concerned the hydrate water coordinating Ca which was removed and replaced by the carbonate oxygens. The study shows that ACC obtained from different starting solutions show specific local order. Freeze drying leads to solid ACC powder which still contain considerable amounts of hydrate water. Structural subunits are distinct in ACC and different from the crystalline phase. The study supplements recent reports presented by Konrad et al., Purgstaller et al., and Tobler et al.. F. Konrad et al., Cryst. Growth Des. 16, 6310-6317(2016) B. Purgstaller et al., Geochimica et Cosmochimica

Hydrogen storage in new nano-structured carbonic materials is a topic for lively discussion. The measured storage capacities of these materials, which have been announced in the literature during the last ten years are spread over an enormous range from about 0.1 wt% up to 67 wt%. This paper will give a report on the state of the art of hydrogen storage in carbon nano-structures. We shall critically review the recent 'key publications' on this topic, which claim storage capacities clearly above the technological bench mark set by the US Department of Energy, and we shall report new results which have been obtained in a joint project sponsored by the Federal Ministry for Education and Research in Germany (BMBF). (authors)

We report the SiO 2 /SiO X /SiO X N Y (OO X O N ) stacked nonvolatile memory (NVM) using hydrogenatedamorphous silicon germanium (a-Si X Ge 1–X :H) as an active channel layer. In NVMs, the reduction of interface trap density is one of the key issues to improve device performance including memory window and retention. The NVMs using a-SiGe:H as the active channel overcame the limitation of small memory window size and poor retention characteristics by controlling the interface trap density using different Ge contents in the surface SiGe layer. For a-Si:H NVM that does not contain Ge, the memory size is about 5.15 V, which is quite large, with a programming voltage of −7 V and an erasing voltage of +15 V. However, the retention time of over 10 years is almost impossible. For a-SiGe:H NVM with 20% Ge, the memory size is as large as 7.38 V and the retention data of ∼58% is possible even after 10 years due to the reduced trap density in OO X O N and channel layers. When the Ge content is more than 20%, the memory size and retention property after 10 years decrease rapidly. When the contents of Ge in SiGe films reach a certain point, they act as defects lowering the properties. The results of NVM devices using a-SiGe:H (Ge 20%) as an active channel layer demonstrate that they have switching characteristics suitable for data storage such as a threshold voltage window. (paper)

Highlights: • a-C:Ti nanocomposite coatings were prepared on 316L stainless steel by using R.F. magnetron sputtering method. • Properties of the nanocomposite coatings were analyzed with respect to titanium content. • Corrosion resistance, biocompatibility and hydrophobicity of nanocomposite coating were enhanced with increasing titanium content. • Coating with 2.33 at.% titanium showed superior tribological properties compared to other coatings. - Abstract: Amorphouscarbon incorporated with titanium (a-C:Ti) was coated on 316L stainless steel (SS) by magnetron sputtering technique to attain superior tribological properties, corrosion resistance and biocompatibility. The morphology, topography and functional groups of the nanostructured a-C:Ti coatings in various concentrations were analyzed using atomic force microscopy (AFM), Raman, X-Ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Raman and XPS analyses confirmed the increase in sp{sup 2} bonds with increasing titanium content in the a-C matrix. TEM analysis confirmed the composite nature of the coating and the presence of nanostructured TiC for Ti content of 2.33 at.%. This coating showed superior tribological properties compared to the other a-C:Ti coatings. Furthermore, electrochemical corrosion studies were performed against stimulated body fluid medium in which all the a-C:Ti coatings showed improved corrosion resistance than the pure a-C coating. Preosteoblasts proliferation and viability on the specimens were tested and the results showed that a-C:Ti coatings with relatively high Ti (3.77 at.%) content had better biocompatibility. Based on the results of this work, highly durable coatings with good biocompatibility could be achieved by incorporation of optimum amount of Ti in a-C coatings deposited on SS by magnetron sputtering technique.

Earth-abundant, low-cost electrocatalysts with outstanding catalytic activity in the electrochemical hydrogen evolution reaction (HER) are critical in realizing the hydrogen economy to lift our future welfare and civilization. Here we report that excellent HER activity has been achieved with three-dimensional core/shell Co/Co3O4 nanosheets composed of a metallic cobalt core and an amorphous cobalt oxide shell. A benchmark HER current density of 10 mA cm(-2) has been achieved at an overpotential of ∼90 mV in 1 M KOH. The excellent activity is enabled with the unique metal/oxide core/shell structure, which allows high electrical conductivity in the core and high catalytic activity on the shell. This finding may open a door to the design and fabrication of earth-abundant, low-cost metal oxide electrocatalysts with satisfactory hydrogen evolution reaction activities.

The purpose of this research is to development the technology required for producing 3-D nano-engineered frameworks for hydrogen storage based on sp2carbon media, which will have high gravimetric and especially high volumetric uptake of hydrogen, and in an aligned fibrous array that will take advantage of the exceptionally high thermal conductivity of sp2carbon materials to speed up the fueling process while minimizing or eliminating the need for internal cooling systems. A limitation for nearly all storage media using physisorption of the hydrogen molecule is the large amount of surface area (SA) occupied by each H2 molecule due to its large zero-point vibrational energy. This creates a conundrum that in order to maximize SA, the physisorption media is made more tenuous and the density is decreased, usually well below 1 kg/L, so that there comes a tradeoff between volumetric and gravimetric uptake. Our major goal was to develop a new type of media with high density H2 uptake, which favors volumetric storage and which, in turn, has the capability to meet the ultimate DoE H2 goals.

Full Text Available The aim of this study was to develop an effective carbonaceous solid acid for synthesizing green fuel additive through esterification of lignocellulose-derived levulinic acid (LA and n-butanol. Two different sulfonated carbons were prepared from glucose-derived amorphouscarbon (GC400 and commercial active carbon (AC400. They were contrastively studied by a series of characterizations (N2 adsorption, X-ray diffraction, elemental analysis, transmission electron microscopy, Fourier transform infrared spectroscopy and NH3 temperature programmed desorption. The results indicated that GC400 possessed stronger acidity and higher –SO3H density than AC400, and the amorphous structure qualified GC400 for good swelling capacity in the reaction solution. Assessment experiments showed that GC400 displayed remarkably higher catalytic efficiency than AC400 and other typical solid acids (HZSM-5, Hβ, Amberlyst-15 and Nafion-212 resin. Up to 90.5% conversion of LA and 100% selectivity of n-butyl levulinate could be obtained on GC400 under the optimal reaction conditions. The sulfonated carbon retained 92% of its original catalytic activity even after five cycles.

The storage of hydrogen is one of the points of development in industrial applications of fuel cells (CAP) of type PEMFC (Proton Exchange Membrane Fuel Cell). An effective system of storage would be a major step in the large scale utilization of this energy source. Process improvements concerning the storage density of energy, the cost, and facilities and the reliability of the storage must be sought in particular for the mobile applications. Among the different approaches possible, the absorption on carbon nanotubes, the production by hydrides in the organic solutions or storage hyperbar in the gas state seems the most promising way.The storage of hydrogen gas at ambient temperature today appears as the technical solution simplest, more advanced and more economic. However the energy density of hydrogen being weaker than that of the traditional fuels, of the quantities more important must be stored at equivalent rate. Hyperbar storage (higher pressure has 350 bar) of hydrogen makes it possible to reduce the volume of the tanks and strengthens the argument for their weights and cost

A continuous hydrogenation device was evaluated for the detoxification of selected tri-, tetra-, or pentacyclic polyaromatic hydrocarbon (PAH) compounds {anthracene, phenanthrene, chrysene, and benzo[a]pyrene (B[a]P)} by hydrogenation. A substrate stream in hexane, 0.05-1.0% (w/v), was mixed with hydrogen-carbon dioxide (H2-CO2, 5-30% v/v) and delivered to a heated reactor column (25 cm x 1 cm) containing palladium supported on gamma alumina (Pd0/gamma-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, approximately 800 mL min(-1) decompressed gas, corresponded to 4 mL min(-1) fluid under the operating conditions of the trials. Reaction products were recovered by passing the reactor effluent through hexane. At 90 degrees C, the anthracene or phenanthrene substrate was hydrogenated only partially to octahydro and dodecahydro species and contained only a minor quantity of totally hydrogenated products. For substrates with increasing numbers of fused aromatic rings, the hydrogenation efficiency was decreased further. However, at an increasing temperature (90-150 degrees C) and increasing mobile phase flow rate (20.68 MPa corresponding to 2100 mL min(-1) decompressed gas), B[a]P and chrysene were hydrogenated, virtuallytotally, to their corresponding perhydro analogues (eicosahydrobenzo[a]pyrenes and octadecahydrochrysenes), respectively. That this approach might be useful for decontaminating soil extracts was supported by companion in vitro trials in which the substrate and products were assayed for mutagenic activity with five bacterial strains that are auxotrophic for histidine (Salmonella typhimurium TA98, TA100, TA1535, and TA1537) or tryptophan (Escherichia coliWP2 uvrA), using the bacterial reverse mutation assay (modified Ames test). Generally, substantial increases in revertant colony counts were not observed with any of the strains following exposure to the hydrogenation products in the absence or presence of the 10 or 30

Owing to the increasing emissions of carbon dioxide (CO(2)), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO(2) in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO(2). Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO(2), offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO(2) not only reduces the increasing CO(2) buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide . The carbon dioxide and hydrogen may be used to produce hydrocarbons....acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H.sup. ions for Na.sup. ions. Carbon dioxide may be

The goal of this work was the study, development and optimization of hydrogenatedamorphous silicon (a-Si:H) devices for use in detection of ionizing radiation. Thick p-i-n devices, capable of withstanding large electric fields (up to 10{sup 6} V/cm) with small currents (nA/cm{sup 2}), were developed. To decrease fabrication time, films were made using the `He diluted` PECVD process and compared to standard a-Si:H films. Aspects connected to specific detector applications as well as to the fundamental physics of a-Si:H were considered: the internal electric field technique, in which the depletion charge was measured as a function of the applied bias voltage; study of the leakage current of p-i-n devices permitted us to demonstrate different regimes: depletion, field-enhanced thermal generation and electronic injection across the p layer. The effect of the electric field on the thermal generation of the carriers was studied considering the Poole-Frenkel and tunneling mechanisms. A model was developed taking under consideration the statistics of the correlated states and electron-phonon coupling. The results suggest that mechanisms not included in the `standard model` of a Si:h need to be considered, such as defect relaxation, a filed-dependent mobility edge etc...; a new metastable phenomenon, induced by prolonged exposure to a strong electric field, was observed and studied. It is characterized by marked decrease of the leakage current and the detector noise, and increase in the breakdown voltage, as well as an improvement of carrier collection efficiency. This forming process appears to be principally due to an activation of the dopants in the p layer; finally, the capacity of thick p-i-n a Si:H devices to detect ionizing radiation has been evaluated. We show that it is possible, with 20-50 micron thick p-i-n devices, to detect the full spectrum of alpha and beta particles. With an appropriate converter, neutron detection then becomes possible. (author). 137 refs.

Direct growth of graphene films on glass is of great importance but has so far met with limited success. The non-catalytic property of glass results in the low decomposition ability of hydrocarbon precursors, especially at reduced temperatures (structural and electrical properties of carbon films deposited on quartz glass at 850 °C by hot-filament chemical vapor deposition (HFCVD). The results revealed that the obtained a-C films were all graphite-like carbon films. Structural transition of the deposited films from a-C to nanocrystalline graphene was achieved by raising the hydrogen dilution ratios from 10 % to over 80 %. Based on systematically structural and chemical characterizations, a schematic process with three steps including sp2 chains aggregation, aromatic rings formation and sp3 bonds etch was proposed to interpret the structural evolution. The nanocrystalline graphene films grown on glass by HFCVD exhibited good electrical performance with a carrier mobility of 36.76 cm2/(V·s) and a resistivity of 5.24×10-3 Ω·cm over an area of 1 cm2. Temperature-dependent electrical characterizations revealed that the electronic transport in carbon films was dominated by defect, localised and extended states respectively when increasing the temperature from 75 K to 292 K. The nanocrystalline graphene films presented higher carrier mobility and lower carrier concentration than a-C films, which was mainly attributed to their smaller conductive activation energy. The present investigation provides an effective way for direct growth of graphene films on glass at reduced temperatures and also offers useful insights into the understanding of structural and electrical relationship between a-C and graphene.

Mechanism of methanol synthesis from carbon monoxide and hydrogen (in the presence of CO 2 ) on various catalysts using radioactive carbon oxides C 14 O and C 14 O 2 was investigated. In the presence of copper-zinc-aluminum and zinc-chromium oxides the methanol synthesis from CO and H 2 occurs via carbon dioxide intermediacy. On a fused iron catalyst the synthesis from carbon monoxide and hydrogen is the main rout to get the lowest alcohols

The objective of the project was to develop a novel complementary membrane reactor process that can consolidate two or more downstream unit operations of a coal gasification system into a single module for production of a pure stream of hydrogen and a pure stream of carbon dioxide. The overall goals were to achieve higher hydrogen production efficiencies, lower capital costs and a smaller overall footprint than what could be achieved by utilizing separate components for each required unit process/operation in conventional coal-to-hydrogen systems. Specifically, this project was to develop a novel membrane reactor process that combines hydrogen sulfide removal, hydrogen separation, carbon dioxide separation and water-gas shift reaction into a single membrane configuration. The carbon monoxide conversion of the water-gas-shift reaction from the coal-derived syngas stream is enhanced by the complementary use of two membranes within a single reactor to separate hydrogen and carbon dioxide. Consequently, hydrogen production efficiency is increased. The single membrane reactor configuration produces a pure H{sub 2} product and a pure CO{sub 2} permeate stream that is ready for sequestration. This project focused on developing a new class of CO{sub 2}-selective membranes for this new process concept. Several approaches to make CO{sub 2}-selective membranes for high-temperature applications have been tested. Membrane disks using the technique of powder pressing and high temperature sintering were successfully fabricated. The powders were either metal oxide or metal carbonate materials. Experiments on CO{sub 2} permeation testing were also performed in the temperature range of 790 to 940 C for the metal carbonate membrane disks. However, no CO{sub 2} permeation rate could be measured, probably due to very slow CO{sub 2} diffusion in the solid state carbonates. To improve the permeation of CO{sub 2}, one approach is to make membranes containing liquid or molten carbonates

Recent advances in high-resolution imaging show the widespreadd occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015, Science). For example, carbonate biomineralization often involves precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that subsequently transforms to crystalline products with diverse structures. Although current carbonate mineral proxies are based upon the composition of final crystalline products, the final signatures may be recording the properties of the initial amorphous phase. Thus, it is critical to establish the physical properties of ACC and understand the factors that influence its evolution to final products at conditions that approximate biological environments. This disconnect limits our ability to build a process-based understanding of when/how minor and trace elements are recorded in mineral composition proxies. In this experimental study, we quantified the chemical and physical properties of ACC and its evolution to final products. We first determined ACC solubility under controlled chemical conditions using a new type of flow-through reactor developed by our research group (Blue and Dove, 2015, GCA; Blue et al., 2017, GCA). The experimental design varied Mg concentration and total alkalinity while maintaining a mild pH that approximates biological environments. ACC solubility was measured at specific time points during the precipitation (from super- and undersaturated conditions) and during its subsequent evolution. Parallel experiments characterized the structure of the corresponding amorphous products using in situ pair distribution function (PDF) and small-angle x-ray scattering (SAXS) analyses. The measurements demonstrate at least two types of ACC can be produced by tuning Mg concentration and alkalinity. Each "phase" exhibits distinct short-range ordering that demonstrates structure-specific solubility. We also find temporal changes in the

Three distinct heterogeneous polymer modification reactions are explored in this work. The first is a bulk reaction commonly conducted on polyolefins---the free radical addition of maleic anhydride. This reaction was run using supercritical carbon dioxide (SC CO2) as the solvent. The second was the chemical surface modification of an amorphous fluorocopolymer of tetrafluoroethylene and a perfluorodioxole monomer (Teflon AF). Several reactions were explored to reduce the surface of the fluorocopolymer for the enhancement of wettability. The last modification was also on Teflon AF and involved the physical modification of the surface through the transport polymerization of xylylene in order to synthesize a novel bilayer membrane. The bulk maleation of poly-4-methyl-1-pentene (PMP) was the focus of the first project. SC CO2 was utilized as both solvent and swelling agent to promote this heterogeneous reaction and led to successful grafting of anhydride groups on both PMP and linear low density polyethylene. Varying the reaction conditions and reagent concentrations allowed optimization of the reaction. The grafted anhydride units were found to exist as single maleic and succinic grafts, and the PMP became crosslinked upon maleation. The surface of a fluoropolymer can be difficult to alter. An examination of three reactions was made to determine the reactivity of Teflon AF: sodium naphthalenide treatment (Na-Nap), aluminum metal modification through deposition and dissolution, and mercury/ammonia photosensitization. The fluorocopolymer with the lower perfluorodioxole percentage was found to be more reactive towards modification with the Na-Nap treatment. The other modification reactions appeared to be nearly equally reactive toward both fluorocopolymers. The functionality of the Na-Nap-treated surface was examined in detail with the use of several derivatization reactions. In the final project, an asymmetric gas separation membrane was synthesized using Teflon AF as

Mg 60 Ni 30 La 10−x Co x (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. It can be found that the smaller activation energy (ΔΕ) and frequency factor (υ 0 ), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg 60 Ni 30 La 10−x Co x (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K

The purpose of the project “Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage” is the development of materials that store hydrogen (H2) by adsorption in quantities and at conditions that outperform current compressed-gas H2 storage systems for electric power generation from hydrogen fuel cells (HFCs). Prominent areas of interest for HFCs are light-duty vehicles (“hydrogen cars”) and replacement of batteries with HFC systems in a wide spectrum of applications, ranging from forklifts to unmanned areal vehicles to portable power sources. State-of-the-art compressed H2 tanks operate at pressures between 350 and 700 bar at ambient temperature and store 3-4 percent of H2 by weight (wt%) and less than 25 grams of H2 per liter (g/L) of tank volume. Thus, the purpose of the project is to engineer adsorbents that achieve storage capacities better than compressed H2 at pressures less than 350 bar. Adsorption holds H2 molecules as a high-density film on the surface of a solid at low pressure, by virtue of attractive surface-gas interactions. At a given pressure, the density of the adsorbed film is the higher the stronger the binding of the molecules to the surface is (high binding energies). Thus, critical for high storage capacities are high surface areas, high binding energies, and low void fractions (high void fractions, such as in interstitial space between adsorbent particles, “waste” storage volume by holding hydrogen as non-adsorbed gas). Coexistence of high surface area and low void fraction makes the ideal adsorbent a nanoporous monolith, with pores wide enough to hold high-density hydrogen films, narrow enough to minimize storage as non-adsorbed gas, and thin walls between pores to minimize the volume occupied by solid instead of hydrogen. A monolith can be machined to fit into a rectangular tank (low pressure, conformable tank), cylindrical tank

As a part of the component development process for the particle bed reactor (PBR), it is necessary to develop coatings which will be time and temperature stable at extremely high temperatures in flowing hydrogen. These coatings must protect the underlying carbon structure from attack by the hydrogen coolant. Degradation which causes small changes in the reactor component, e.g. hole diameter in the hot frit, can have a profound effect on operation. The ability of a component to withstand repeated temperature cycles is also a coating development issue. Coatings which crack or spall under these conditions would be unacceptable. While refractory carbides appear to be the coating material of choice for carbon substrates being used in PBR components, the method of applying these coatings can have a large effect on their performance. Two deposition processes for these refractory carbides, chemical vapor deposition (CVD) and chemical vapor reaction (CVR), have been evaluated. Screening tests for these coatings consisted of testing of coated 2-D and 3-D weave carbon-carbon in flowing hot hydrogen at one atmosphere. Carbon loss from these samples was measured as a function of time. Exposure temperatures up to 3,000 K were used, and samples were exposed in a cyclical fashion cooling to room temperature between exposures. The results of these measurements are presented along with an evaluation of the relative merits of CVR and CVD coatings for this application.

Photocatalysis has not found widespread industrial adoption, in spite of decades of active research, because the challenges associated with catalyst illumination and turnover outweigh the touted advantages of replacing heat with light. A demonstration that light can control product selectivity in complex chemical reactions could prove to be transformative. Here, we show how the recently demonstrated plasmonic behaviour of rhodium nanoparticles profoundly improves their already excellent catalytic properties by simultaneously reducing the activation energy and selectively producing a desired but kinetically unfavourable product for the important carbon dioxide hydrogenation reaction. Methane is almost exclusively produced when rhodium nanoparticles are mildly illuminated as hot electrons are injected into the anti-bonding orbital of a critical intermediate, while carbon monoxide and methane are equally produced without illumination. The reduced activation energy and super-linear dependence on light intensity cause the unheated photocatalytic methane production rate to exceed the thermocatalytic rate at 350 °C. PMID:28230100

Photocatalysis has not found widespread industrial adoption, in spite of decades of active research, because the challenges associated with catalyst illumination and turnover outweigh the touted advantages of replacing heat with light. A demonstration that light can control product selectivity in complex chemical reactions could prove to be transformative. Here, we show how the recently demonstrated plasmonic behaviour of rhodium nanoparticles profoundly improves their already excellent catalytic properties by simultaneously reducing the activation energy and selectively producing a desired but kinetically unfavourable product for the important carbon dioxide hydrogenation reaction. Methane is almost exclusively produced when rhodium nanoparticles are mildly illuminated as hot electrons are injected into the anti-bonding orbital of a critical intermediate, while carbon monoxide and methane are equally produced without illumination. The reduced activation energy and super-linear dependence on light intensity cause the unheated photocatalytic methane production rate to exceed the thermocatalytic rate at 350 °C.

Heterojunctions made of hydrogenatedamorphous silicon (a-Si:H) and crystalline silicon (c-Si) are examined by conducting probe atomic force microscopy. Conductive channels at both (n )a-Si:H/(p)c-Si and (p)a-Si:H/(n)c-Si interfaces are clearly revealed. These are attributed to two-dimension electron and hole gases due to strong inversion layers at the c-Si surface in agreement with previous planar conductance measurements. The presence of a hole gas in (p )a-Si:H/(n)c-Si structures implies a quite large valence band offset (EVc-Si-EVa-Si:H>0.25 eV).

Thermodynamic stability of the hydrogenatedcarbon nanotubes has been explored in the chemisorption limit. Statistical physics and density functional theory calculations have been used to predict hydrogen release temperatures at standard pressure in zigzag and armchair carbon nanotubes. It is found that hydrogen release temperatures decrease with increase in diameters of hydrogenated zigzag carbon nanotubes (CNTs) but opposite trend is noted in armchair CNTs at standard pressure of 1 bar. The smaller diameter hydrogenated zigzag CNTs have large values of hydrogen release temperature due to the stability of Csbnd H bonds. The vibrational density of states for hydrogenatedcarbon nanotubes have been calculated to confirm the Csbnd H stretching mode caused by sp3 hybridization.

Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run the reac......Hydrogen peroxide is a commodity chemical, as it is an environmentally friendly oxidant. The electrochemical production of H2O2 from oxygen and water by the reduction of oxygen is of great interest, as it would allow the decentralized, on-site, production of pure H2O2. The ability to run...... the reaction in an acidic electrolyte with high performance is particularly important, as it would allow the use of polymer solid electrolytes and the production of pH-neutral hydrogen peroxide. Carbon catalysts, which are cheap, abundant, durable and can be highly selective show promise as potential catalysts...... to determine the cause of these differences, we employ prompt gamma ray/neutron activation analysis and XPS measurements to assess the contribution of heteroatoms and defects, as well as low temperature N2-adsorption and transmission electron microscopy to elucidate the particle size, shape, BET surface area...

An experimental rig program was conducted with the objective of evaluating the combuston performance of a family of fuel gases based on a mixture of hydrogen and carbon monoxide. These gases, in addition to being members of a family, were also representative of those secondary fuels that could be produced from coal by various gasification schemes. In particular, simulated Winkler, Lurgi, and Blue-water low and medium energy content gases were used as fuels in the experimental combustor rig. The combustor used was originally designed as a low NOx rich-lean system for burning liquid fuels with high bound nitrogen levels. When used with the above gaseous fuels this combustor was operated in a lean-lean mode with ultra long residence times. The Blue-water gas was also operated in a rich-lean mode. The results of these tests indicate the possibility of the existence of an 'optimum' gas turbine hydrogen - carbon monoxide based secondary fuel. Such a fuel would exhibit NOx and high efficiency over the entire engine operating range. It would also have sufficient stability range to allow normal light-off and engine acceleration. Solar Turbines Incorporated would like to emphasize that the results presented here have been obtained with experimental rig combustors. The technologies generated could, however, be utilized in future commercial gas turbines.

Amorphouscarbon is regarded as a promising alternative to commercial graphite as the lithium-ion battery anode due to its capability to reversibly store more lithium ions. However, the structural disorder with a large number of defects can lead to low electrical conductivity of the amorphouscarbon, thus limiting its application for high power output. Herein, ultrathin amorphouscarbon nanosheets were prepared from petroleum asphalt through tuning the carbonization temperature in a molten-salt medium. The amorphous nanostructure with expanded carbon interlayer spacing can provide substantial active sites for lithium storage, while the two-dimensional (2D) morphology can facilitate fast electrical conductivity. As a result, the electrodes deliver a high reversible capacity, outstanding rate capability, and superior cycling performance (579 and 396 mAh g -1 at 2 and 5 A g -1 after 900 cycles). Furthermore, full cells consisting of the carbon anodes coupled with LiMn 2 O 4 cathodes exhibit high specific capacity (608 mAh g -1 at 50 mA g -1 ) and impressive cycling stability with slow capacity loss (0.16% per cycle at 200 mA g -1 ). The present study not only paves the way for industrial-scale synthesis of advanced carbon materials for lithium-ion batteries but also deepens the fundamental understanding of the intrinsic mechanism of the molten-salt method.

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

The performance of various carbon-based materials in flowing, high-temperature helium and hydrogen is described. These materials which are candidate hot frit substrates for possible application in a PBR include various grades of graphite, carbon-carbon and vitreous carbon. Vitreous carbon showed extremely good performance in helium, while that of the various graphite grades was quite variable and, in some cases, poor. Purified grades performed better than unpurified grades, but in all cases large sample-to-sample variations in weight loss were observed. For carbon-carbon samples, the performance was intermediate. Since the weight loss in these samples was in large measure due to the loss of the densification media, improvements in the performance of carbon-carbon may be possible. With respect to the performance in hydrogen, high weight losses were observed, re-enforcing the need for coating carbon-based materials for service in a flowing hydrogen environment

Carbon dioxide conversion and utilization is gaining significant attention worldwide, not only because carbon dioxide has an impact on global climate change, but also because it provides a source for potential fuels and chemicals. Methanol is an important fuel that can be obtained by the hydrogenation of carbon dioxide. In this research, the modeling of a reactor to produce methanol using carbon dioxide and hydrogen is carried out by way of an ANOVA and a central composite design. Reaction te...

The photoactivity of g-C3N4 is greatly limited by its high recombination rate of photogenerated carriers. Coupling g-C3N4 with other materials has been demonstrated to be an effective way to facilitate the separation and transport of charge carriers. Herein we report a composite of conductive carbon black and carbon nitride intercalation compound synthesized through facile one-step molten salt method. The as-prepared carbon black/carbon nitride intercalation compound composite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), UV-vis absorption spectrum and photoluminescence spectroscopy (PL). The carbon black nanoparticles, homogeneously dispersed on the surface of carbon nitride intercalation compound, efficiently enhanced separation and transport of photogenerated carriers, thus improving the visible-light photocatalytic activity. The composite of 0.5 wt% carbon black and carbon nitride intercalation compound exhibited a H2 production rate of 68.9 μmol h(-1), which is about 3.2 times higher than hydrogen production on pristine carbon nitride intercalation compound.

The aim of this work is to build and calibrate an experimental set-up for the testing of the materials, to produce some carbon materials in large amounts and characterise them, and finally, to test these materials in their ability to store hydrogen. This will help in establishing a link between the hydrogen storage capacities of the carbons and their nano-structure. The script is divided into four chapters. The first chapter will deal with the literature review on the thematic of hydrogen storage through adsorption in the carbon materials, while the second chapter will present the experimental set-up elaborated in the laboratory. The third chapter explains the processes used to produce the two families of carbon materials and finally, the last chapter presents the structural characterisation of the samples as well as the experimental results of hydrogen storage on the materials elaborated. (author)

In this paper we review the existing theoretical literature on hydrogen storage in single-walled nanotubes and carbon nanofibers. The reported calculations indicate a hydrogen uptake smaller than some of the more optimistic experimental results. Furthermore the calculations suggest that a variety of complex chemical processes could accompany hydrogen storage and release. (orig.)

In this work, we aim at exploring using ab initio calculations, the various ways allowing for an efficient hydrogen docking in carbon porous materials. Firstly, the influence of surface curvature on the chemisorption of atomic hydrogen is considered. Then it is shown that electro-donor elements such as lithium or potassium used as dopant of the carbon substrate induce a strong physi-sorption for H{sub 2}, allowing its storage at ambient temperature under moderate pressure. (authors)

The sandwich-like nickel/palladium/carbon electrodes exhibiting ability to absorb hydrogen in alkaline solution are presented. Electrodes were prepared by successive deposition of palladium and polyaniline layers on nickel foam substrate followed by heat treatment to give Ni/Pd/C electrode. It was shown that thermal conversion of polymer into carbon layer and subsequent thermal activation of carbon component bring about the modification of the mechanism of reversible hydrogen sorption. It was proven that carbon layer, interacting with Pd catalyst, plays a considerable role in the process of hydrogen storage. In the other series of experiments, Pd particles were dispersed electrochemically on carbon coating leading to Ni/C/Pd system. The adding of the next carbon layer resulted in Ni/C/Pd/C electrodes. Electrochemical properties of the electrodes depend on both the sequence of Pd and C layers and the preparation/activation of carbon coating. Electrochemical behavior of sandwich-like electrodes in the reaction of hydrogen sorption/desorption was characterized in 6 M KOH using the cyclic voltammetry method and the results obtained were compared to those for Ni/Pd electrode. The anodic desorption of hydrogen from electrodes free and containing carbon layer was considered after the potentiodynamic as well as potentiostatic sorption of hydrogen. The influence of the sorption potential and the time of rest of electrodes at a cut-off circuit on the kinetics of hydrogen recovery were examined. The results obtained for Ni/Pd/C electrodes indicate that the displacement of hydrogen between C and Pd phase takes place during the rest at a cut-off circuit. Electrodes containing carbon layer require longer time for hydrogen electrosorption. On the other hand, the presence of carbon layer in electrodes is advantageous because a considerable longer retention of hydrogen is possible, as compared to Pd/Ni electrode. Hydrogen stored in sandwich-like electrodes can instantly be

A simple hydrogen adsorption measurement system utilizing the volumetric differential pressure technique has been designed, fabricated and calibrated. Hydrogen adsorption measurements have been carried out at temperatures 298 K and 77 K on activate carbon and carbon nanotubes with different surface areas. The adsorption data obtained will be helpful in understanding the adsorption property of the studied carbon materials using the fundamentals of adsorption theory. The principle of the system follows the Sievert-type method. The system measures a change in pressure between the reference cell, R1 and the sample cell S1, S2, S3 over a certain temperature range, R1, S1, S2, and S3 having known fixed volume. The sample temperatures will be monitored by thermocouple TC while the pressures in R1 an S1, S2, S3 will be measured using a digital pressure transducer. The maximum operating pressure of the pressure transducer is 20 bar and calibrated with an accuracy of ±0.01 bar. High purity hydrogen is being used in the system and the amount of samples for the study is between 1.0-2.0 grams. The system was calibrated using helium gas without any samples in S1, S2 an S3. This will provide a correction factor during the adsorption process providing an adsorption free reference point when using hydrogen gas resulting in a more accurate reading of the adsorption process by eliminating the errors caused by temperature expansion effects and other non-adsorption related phenomena. The ideal gas equation of state is applied to calculate the hydrogen adsorption capacity based on the differential pressure measurements. Activated carbon with a surface area of 644.87 m 2 /g showed a larger amount of adsorption as compared to multiwalled nanotubes (commercial) with a surface area of 119.68 m 2 /g. This study als indicated that there is a direct correlation between the amounts of hydrogen adsorbed an surface area of the carbon materials under the conditions studied and that the adsorption

An existing industrial hydrogen generation and distribution infrastructure is described, and a number of large-scale investment projects are outlined. All of these projects have the potential to generate significant volumes of low-cost, low-carbonhydrogen. The technologies concerned range from gasification of coal with carbon capture and storage…

Carbon dioxide hydrogenation to form hydrocarbons was conducted on two iron-based catalysts, prepared according to procedures described in the literature, and on a new iron spinel catalyst. The CO2 conversion measured in a packed-bed reactor was limited to about 60% because of excessive amounts of water produced in this process. Switching to a system of three packed-bed reactors in series with interim removal of water and condensed hydrocarbons increased CO2 conversion to as much as 89%. The pure spinel catalyst displayed a significantly higher activity and selectivity than those of the other iron catalysts. This process produces a product called green feed, which is similar in composition to the product of a high-temperature, iron-based Fischer–Tropsch process from syngas. The green feed can be readily converted into renewable fuels by well-established technologies.

The idea of a "Hydrogen Economy" is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO₂ in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H₂ from the electrolyzer. Methanol made with CO₂ from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

In this study, we focused on sericin hydrolysates, originating from silkworm used in serum-free human bone marrow-derived mesenchymal stem cells (hBM-MSCs) culture. We reported the effect of a covalent linkage between a bioactive protein molecule and polystyrene dish surface via a carbon intermediate layer which can slow down the release rate of protein compounds into the phosphate buffer saline (PBS) solution. Films of amorphouscarbon (a-C) and functionalized-carbon were deposited on PS culture dish surfaces by using a DC magnetron sputtering system and RF PECVD system. We found that a-C based-films can increase the hydrophilicity and biocompatibility of polystyrene (PS) dishes, especially a-C films and a-C:N2 films showed good attachment of hBM-MSCs at 24 h. However, in the case of silica surface (a-C:SiOx films), the cells showed a ragged and unattached boundary resulting from the presence of surface silanol groups. For the UV-vis absorbance, all carbon modified-PS dishes showed a lower release rate of sericin molecules into PBS solution than PS control. This revealed that the functionalized carbon could be enhanced by specific binding properties with given molecules. The carbon-coated PS dishes grafting with sericin protein were used in a serum-free condition. We also found that hBM-MSCs have higher percentage of proliferated cells at day 7 for the modified dishes with carbon films and coated with sericin than the PS control coated with sericin. The physical film properties were measured by atomic force microscopy (AFM), scanning electron microscope (SEM) and contact angle measurement. The presence of sbnd NH2 groups of sericin compounds on the PS dish was revealed by Fourier transform infrared spectroscopy (FTIR). The stability of covalent bonds of sericin molecules after washing out ungrafted sericin was confirmed by X-ray photoelectron spectroscopy (XPS).

In this study, we focused on sericin hydrolysates, originating from silkworm used in serum-free human bone marrow-derived mesenchymal stem cells (hBM-MSCs) culture. We reported the effect of a covalent linkage between a bioactive protein molecule and polystyrene dish surface via a carbon intermediate layer which can slow down the release rate of protein compounds into the phosphate buffer saline (PBS) solution. Films of amorphouscarbon (a-C) and functionalized-carbon were deposited on PS culture dish surfaces by using a DC magnetron sputtering system and RF PECVD system. We found that a-C based-films can increase the hydrophilicity and biocompatibility of polystyrene (PS) dishes, especially a-C films and a-C:N{sub 2} films showed good attachment of hBM-MSCs at 24 h. However, in the case of silica surface (a-C:SiO{sub x} films), the cells showed a ragged and unattached boundary resulting from the presence of surface silanol groups. For the UV–vis absorbance, all carbon modified-PS dishes showed a lower release rate of sericin molecules into PBS solution than PS control. This revealed that the functionalized carbon could be enhanced by specific binding properties with given molecules. The carbon-coated PS dishes grafting with sericin protein were used in a serum-free condition. We also found that hBM-MSCs have higher percentage of proliferated cells at day 7 for the modified dishes with carbon films and coated with sericin than the PS control coated with sericin. The physical film properties were measured by atomic force microscopy (AFM), scanning electron microscope (SEM) and contact angle measurement. The presence of -NH{sub 2} groups of sericin compounds on the PS dish was revealed by Fourier transform infrared spectroscopy (FTIR). The stability of covalent bonds of sericin molecules after washing out ungrafted sericin was confirmed by X-ray photoelectron spectroscopy (XPS).

In this study, we focused on sericin hydrolysates, originating from silkworm used in serum-free human bone marrow-derived mesenchymal stem cells (hBM-MSCs) culture. We reported the effect of a covalent linkage between a bioactive protein molecule and polystyrene dish surface via a carbon intermediate layer which can slow down the release rate of protein compounds into the phosphate buffer saline (PBS) solution. Films of amorphouscarbon (a-C) and functionalized-carbon were deposited on PS culture dish surfaces by using a DC magnetron sputtering system and RF PECVD system. We found that a-C based-films can increase the hydrophilicity and biocompatibility of polystyrene (PS) dishes, especially a-C films and a-C:N 2 films showed good attachment of hBM-MSCs at 24 h. However, in the case of silica surface (a-C:SiO x films), the cells showed a ragged and unattached boundary resulting from the presence of surface silanol groups. For the UV–vis absorbance, all carbon modified-PS dishes showed a lower release rate of sericin molecules into PBS solution than PS control. This revealed that the functionalized carbon could be enhanced by specific binding properties with given molecules. The carbon-coated PS dishes grafting with sericin protein were used in a serum-free condition. We also found that hBM-MSCs have higher percentage of proliferated cells at day 7 for the modified dishes with carbon films and coated with sericin than the PS control coated with sericin. The physical film properties were measured by atomic force microscopy (AFM), scanning electron microscope (SEM) and contact angle measurement. The presence of -NH 2 groups of sericin compounds on the PS dish was revealed by Fourier transform infrared spectroscopy (FTIR). The stability of covalent bonds of sericin molecules after washing out ungrafted sericin was confirmed by X-ray photoelectron spectroscopy (XPS).

We will demonstrate that carbon particles consisting of large cages can be produced without catalytic metal. The carbon particles were produced in CO gas as well as by introduction of 5% methane gas into the CO gas. The gas-produced carbon particles were able to absorb approximately 16.2 wt% of hydrogen. This value is 2.5 times higher than the 6.5 wt% goal for the vehicular hydrogen storage proposed by the Department of Energy in the USA. Therefore, we believe that this carbon particle is an excellent candidate for hydrogen storage for fuel cells.

Highlights: ► We studied the effect of pH and Mg in the crystallization of amorphous CaCO 3 (ACC). ► The study combined synchrotron-based scattering with electron microscopy. ► The pH-dependent C speciation and hydration strength of Mg 2+ control ACC structure. ► This ACC structure governs the ACC dissolution rate and crystallization pathway. - Abstract: The effects of pH and Mg on the crystallization of amorphous calcium carbonate (ACC) to vaterite and/or calcite were studied using a combination of in situ time resolved synchrotron-based techniques and electron microscopy. The experiments showed that Mg increased the stability of ACC and favoured the formation of calcite over vaterite. A neutral (∼7) starting pH during mixing promoted the transformation of ACC into calcite via a dissolution/reprecipitation mechanism. Conversely, when ACC formed in a solution that started with a high initial pH (∼11.5), the transformation to calcite occurred via metastable vaterite, which formed via a spherulitic growth mechanism. In a second stage this vaterite transformed to calcite via a surface-controlled dissolution and recrystallization mechanism. These crystallization pathways can be explained as a consequence of the pH-dependent composition, local structure, stability and dissolution rates of ACC.

Formation of a liquid phase with a transition to a homogeneous amorphous state under the surface layer solidification is detected under picosecond laser pulse effect on the microcrystalline graphite. A periodic surface structure is produced in the heating region with the period of the order of the length of the heating pulse wave, its strokes following the direction of this pulse polarization. Study of the probing laser pulse reflection kinetics has shown, that the typical time of liquid phase and solidification life makes up ∼ 10 -10 s

Based on the elementary reaction steps for chemical erosion of carbon by hydrogen a model is developed which allows to calculate the amount of carbon erosion at a hydrogenatedcarbon surface under the impact of hydrogen ions and neutrals. Hydrogen ion and neutral flux energy distributions prevailing at target plates in the ASDEX upgrade experiment are chosen in the present calculation. The range of hydrogen particles in the target plates is calculated using TRIDYN code. Based upon the TRIDYN results the extent of the erosion reaction as a function of depth is estimated. The results show that both, target temperature and impinging particle flux energy distribution, determine the hydrogen flux density dependent erosion yield and the location of the erosion below the surface. (orig.)

Sphere-like and layer-by-layer growth mechanisms of polypyrrole are controlled by changing pyrrole monomer concentration and using carbon nanotubes (CNT) as template. Pristine polypyrrole has sphere-like structures but remarkable change in types of polypyrrole growth is observed from spherical-like to layer-by-layer structures in the presence of CNT. Acid treatment enhances polypyrrole coverage on CNT surface by preventing agglomeration of polypyrrole due to an increase in surface oxygen groups and sp{sup 2} bonds in CNT structure. The crystallinity of powders comparably decreases after polypyrrole coating due to the amorphous structure of polypyrrole and a sharp decrease in the intensity of 002 peak. The influence of surface functionalization and polymer coating on the structural parameters of multi-walled CNT and their composites is investigated by tailoring the feeding ratio of polypyrrole. The hydrogen sorption measurements at ambient conditions by Intelligent Gravimetric Analyzer demonstrate that hydrogen uptake of CNT/polypyrrole composite is 1.66 wt.% which is almost 3 times higher than that of pristine CNT. Higher hydrogen uptake values are obtained by keeping the mass ratio of pyrrole monomer and CNT equal by using non-functionalized CNT in composite production. Hydrogen adsorption/desorption kinetics of polypyrrole/CNT composites is improved by increasing adsorption sites after polymer coating and acid treatment. The desorption curves of these modified surfaces are higher than their adsorption curves at lower pressures and hysteresis loop is observed in their isotherms since hydrogen is chemically bonded to the modified surfaces by the conversion of carbon atoms from sp{sup 2} to sp{sup 3} hybridization. - Highlights: • Growth mechanisms of polypyrrole are controlled by changing monomer concentration. • Lamellar structure is formed by using pristine CNT at high monomer concentration. • Homogeneous polymer coating is achieved on the surface of

The effect of temperature on the electron field emission properties of copper incorporated amorphous diamond like carbon (a-Cu:DLC) thin films have been reported. The a-Cu:DLC thin films have been deposited on indium tin oxide (ITO) coated glass and silicon substrate by the radio frequency sputtering process. The chemical composition of the films was investigated using X-ray photoelectron spectroscopy and the micro structure was established using high resolution transmission electron microscopy. The sp2 and sp3 bonding ratio in the a-Cu:DLC have been analyzed by the Fourier transformed infrared spectroscopy studies. The material showed excellent electron field emission properties; which was optimized by varying the copper atomic percentage and temperature of the films. It was found that the threshold field and effective emission barrier were reduced significantly by copper incorporation as well as temperature and a detailed explanation towards emission mechanism has been provided.

Cadmium Selenide (CdSe) quantum dot (QD) decorated amorphouscarbon nanotubes (a-CNTs) hybrids have been synthesized by simple chemical process. The samples were characterized by field emission scanning and transmission electron microscopy, Fourier transformed infrared spectroscopy, Raman and UV-Vis spectroscopy. Lattice image obtained from transmission electron microscopic study confirms the successful attachment of CdSe QDs. It is seen that hybrid samples show an enhanced cold emission properties with good stability. The results have been explained in terms of increased roughness, more numbers of emitting sites and favorable band bending induced electron transport. ANSYS software based calculation has also supported the result. Also a first principle based study has been done which shows that due to the formation of hybrid structure there is a profound upward shift in the Fermi level, i.e. a decrease of work function, which is believed to be another key reason for the observed improved field emission performance.

We discuss in this paper the evolution of both the density of states (DOS) located between the band-tail states and the DOS around the Fermi level N(E F ) in amorphouscarbon nitride films (a-CN x ) as a function of the total nitrogen partial pressure ratio in the Ar/N 2 plasma mixture. The films were deposited by three different deposition techniques and their microstructure was characterized using a combination of infrared and Raman spectroscopy and optical transmission experiments, completed with electrical conductivity measurements, as a function of temperature. The observed changes in the optoelectronic properties are attributed to the modification in the atomic bonding structures, which were induced by N incorporation, accompanied by an increase in the sp 2 carbon bonding configurations and their relative disorder. The electrical conductivity variation was interpreted in terms of local effects on the nature and energy distribution of π and π* states.

Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed.

Full Text Available Tantalum (Ta is a promising metal for biomedical implants or implant coating for orthopedic and dental applications because of its excellent corrosion resistance, fracture toughness, and biocompatibility. This study synthesizes biocompatible tantalum carbide (TaC and TaC/amorphouscarbon (a-C coatings with different carbon contents by using a twin-gun magnetron sputtering system to improve their biological properties and explore potential surgical implant or device applications. The carbon content in the deposited coatings was regulated by controlling the magnetron power ratio of the pure graphite and Ta cathodes. The deposited TaC and TaC/a-C coatings exhibited better cell viability of human osteosarcoma cell line MG-63 than the uncoated Ti and Ta-coated samples. Inverted optical and confocal imaging was used to demonstrate the cell adhesion, distribution, and proliferation of each sample at different time points during the whole culture period. The results show that the TaC/a-C coating, which contained two metastable phases (TaC and a-C, was more biocompatible with MG-63 cells compared to the pure Ta coating. This suggests that the TaC/a-C coatings exhibit a better biocompatible performance for MG-63 cells, and they may improve implant osseointegration in clinics.

We reported a facile and scalable salt-templated approach to produce monodisperse Rh nanoparticles (NPs) on ultrathin carbon nanosheets with the assistance of calcination under inert gas. More importantly, in spite of the essentially poor ORR activity of Rh/C, the acquired Rh/C hybrid nanosheets display a comparable ORR activity to the optimal commercial Pt/C catalyst, which may be due to the extra-small size of Rh NPs and the 2D defect-rich amorphouscarbon nanosheets that can facilitate the charge transfer and reactive surface exposure. Moreover, Rh/C nanosheets present the optimal current density and best durability with the minimum decline during the entire test, so that ∼93% activity after 20 000 s is achieved, indicating a good lifetime for ORR. In contrast, commercial Pt/C and commercial Rh/C exhibited worse durability, so that ∼74% and ∼85% activities after 20 000 s are maintained. What's more, in the model system of reduction of 4-nitrophenol (4-NP), the kinetic constant k for Rh/C nanosheets is 3.1 × 10 -3 , which is 4.5 times than that of the commercial Rh/C catalyst, revealing that our Rh/C hybrid nanosheets can be potentially applied in industrial catalytic hydrogenation. This work opens a novel and facile way for the rest of the precious metal NPs to be supported on ultrathin carbon nanosheets for heterogeneous catalysis.

This thesis describes our research on adsorbent systems for hydrogen storage for small scale, mobile application. Hydrogen storage is a key element in the change-over from the less efficient and polluting internal combustion engine to the pollution-free operating hydrogen fuel cell. In general,

Full Text Available Hydrogen storage has been a key bottle-neck in the actualization of hydrogen as an energy carrier. The new field of hydrogen storage in templated carbonaceous materials has excited many researchers and considerable effort is being directed...

Thin carbon films with various thickness, deposited on different substrates (Si and poly-ethylene-terephthalate) at the same operating conditions in a ratio frequency plasma enhanced chemical vapor deposition system were characterized by Doppler broadening spectroscopy. The films and the substrates were depth profiled by a slow positron beam. The aim od these measurements was to study the open volume structure and the interface of the films. It was found that, independently from the substrate, the films were homogeneous and exhibited to some open volume distribution. On the contrary, the effective positron diffusion length in the Si substrate was found to change with the thickness of the carbon films. This behaviour was found to change with the thickness of the carbon films. This behaviour was interpreted as a change in the electric field at the carbon/silicon interface. (author)

Full Text Available The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan. Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

Here we report direct physical evidence that confinement of molecular hydrogen (H2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H2 at temperatures up to 67 K above the liquid-vapor critical temperature of bulk H2. This extreme densification is attributed to confinement of H2 molecules in the optimally sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorption isotherms. The demonstration of the existence of solid-like H2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.

This paper reports the method of disc pressure test and the results for 21-6-9 stainless steel and medium carbon steel in hydrogen gas with different pressures and time of storage. The results show the hydrogen induced degradation of these two kinds of steel. An attempt was made to establish an index which uses variation of area of deformed disc to determine the degradation of ductility in a hydrogen environment. (orig.)

Activated carbons, thanks to their versatility, are being used in the water treatment sector to absorb pollutants. Several factors influence the adsorption capacity of activated carbon and the aim of this study was to assess the effects of the porous texture and chemical nature of activated carbons on the adsorption of triton X100 and potassium hydrogen phthalate. Activated carbons used in this study were prepared from date pits with ZnCl2, KOH and H3PO4 by carbonization without adjuvant and adsorption of triton X100 and potassium hydrogen phthalate was conducted at 298K. Results showed that activated carbons prepared from date pits have a great potential for removing organic and inorganic pollutants from water and that the adsorption potential depends on the degree of activation of the activated carbons and on the compounds to absorb. This study highlighted that an increase of the carbon surface area and porosity results in a better adsorption capacity.

The aim of this work is to build and calibrate an experimental set-up for the testing of the materials, to produce some carbon materials in large amounts and characterise them, and finally, to test these materials in their ability to store hydrogen. This will help in establishing a link between the hydrogen storage capacities of the carbons and their nano-structure. The script is divided into four chapters. The first chapter will deal with the literature review on the thematic of hydrogen storage through adsorption in the carbon materials, while the second chapter will present the experimental set-up elaborated in the laboratory. The third chapter explains the processes used to produce the two families of carbon materials and finally, the last chapter presents the structural characterisation of the samples as well as the experimental results of hydrogen storage on the materials elaborated. (author)

Full Text Available Nanoporous carbons which possess high surface areas and narrow pore size distributions have become one of the most important classes of porous materials with potential to be utilized for hydrogen storage. In recent times, several metal...

Full Text Available Of the many available options for hydrogen storage, carbonaceous materials are gaining increasing attention. In particular, templated carbons have attracted research interest because of the ability to control their pore structure properties...

The simultaneous removal of carbon dioxide and hydrogen sulphide was studied for agrobiogas pre-treatment, using water–swollen thin hydrophilic film composites (TFC) based on industrially produced membranes.

Heterogeneous selective hydrogenation of ethylene carbonate (EC), a key step in indirect conversion of CO2, was realized over a copper chromite nanocatalyst prepared via a hydrothermal method followed by calcination. The selectivities towards methanol (60%) and ethylene glycol (93%) were higher than those achieved over other usual hydrogenation catalysts.

Full Text Available Molar Incisor Hypomineralization (MIH is characterized by a developmentally derived deficiency in mineral enamel. Affected teeth present demarcated enamel opacities, ranging from white to brown; also hypoplasia can be associated. Patient frequently claims aesthetic discomfort if anterior teeth are involved. This problem leads patients to request a bleaching treatment to improve aestheticconditions.Nevertheless, hydrogen peroxide can produce serious side-effects, resulting from further mineral loss. Microabrasion and/or a composite restoration are the treatments of choice in teeth with mild/moderate MIH, but they also need enamel loss. Recently, a new remineralizing agent based on Casein Phosphopeptide-Amorphous Calcium Phosphate (CPP-ACP has been proposed to be effective in hypomineralized enamel, improving also aesthetic conditions. The present paper presents a case report of a young man with white opacities on incisors treated with a combined use of CPP-ACP mousse and hydrogen peroxide gel to correct the aesthetic defect. The patient was instructed to use CPP-ACP for two hours per day for three months in order to obtain enamel remineralization followed by a combined use of CPP-ACP and bleaching agent for further two months. At the end of this five-month treatment, a noticeable aesthetic improvement of the opacities was observed.

Molar Incisor Hypomineralization (MIH) is characterized by a developmentally derived deficiency in mineral enamel. Affected teeth present demarcated enamel opacities, ranging from white to brown; also hypoplasia can be associated. Patient frequently claims aesthetic discomfort if anterior teeth are involved. This problem leads patients to request a bleaching treatment to improve aestheticconditions.Nevertheless, hydrogen peroxide can produce serious side-effects, resulting from further mineral loss. Microabrasion and/or a composite restoration are the treatments of choice in teeth with mild/moderate MIH, but they also need enamel loss. Recently, a new remineralizing agent based on Casein Phosphopeptide-Amorphous Calcium Phosphate (CPP-ACP) has been proposed to be effective in hypomineralized enamel, improving also aesthetic conditions. The present paper presents a case report of a young man with white opacities on incisors treated with a combined use of CPP-ACP mousse and hydrogen peroxide gel to correct the aesthetic defect. The patient was instructed to use CPP-ACP for two hours per day for three months in order to obtain enamel remineralization followed by a combined use of CPP-ACP and bleaching agent for further two months. At the end of this five-month treatment, a noticeable aesthetic improvement of the opacities was observed. PMID:23243519

Full text:The multi-wall carbon nanotubes (MWNTs) synthesized by plasma enhanced CVD in 0.1% CH 4 (H 2 dilution) reaction gas were shaped in curly structures with the blocked nano-pores and closed caps. On the contrary, the carbon nanotubes with different structures could be obtained in oxygen added reaction gas, showing straight MWNTs with connected pore and open caps. The hydrogen desorption properties of the carbon nanotubes with these closed and open structure were compared by thermal desertion technique. The MWNTs with closed structure desorbed hydrogen at two different temperature ranges such as 290∼325K, and 415∼420K, where the evolved hydrogen amount were 0.64 wt% and 0.03 wt%, respectively. In case of MWNTs with open structure, hydrogen as high as 1.97 wt% was released at 300∼325K. The low temperature hydrogen desertion of multi-wall carbon nanotubes with open and closed structure showed the hydrogen adsorption activation energies of ∼16.52 kJ/mol and 18.49 kJ/mol, respectively. The high temperature hydrogen desorption observed only in carbon nanotube with closed and defective structure was as high desorption activation energy as -124.4 kJ/mol

Measurements made in the tokamak Torus Experiment for Technology Oriented Research (TEXTOR) with carbonized graphite limiters and carbonized Inconel liner (''all carbon machine'') and from a carbonized simulation vessel are presented and discussed with particular emphasis on hydrogen recycling phenomena. The hydrogen recycling during tokamak discharges is strongly affected by the wall temperature. Slow loading or deloading of the wall with hydrogen occurs at low (150 0 C) wall temperatures, whereas stationary conditions are reached rapidly at 350 0 C. At 350 0 C, recycling coefficients smaller than 1 can be achieved. Active density control during tokamak discharges is demonstrated by using the wall pumping effect in combination with shifts of the plasma position. No tendency for saturation of the wall pumping as a function of the discharge number is found when the wall temperature is 350 0 C. A model is presented for the explanation of the observed effects. It involves particle induced desorption, thermal outgassing, and implantation of hydrogen. Particle induced desorption dominates at low temperatures and high hydrogen concentrations in the carbon films, thermal outgassing becomes increasingly important at higher temperatures. Hydrocarbon formation and release at wall areas exposed to high hydrogen fluxes and the codeposition of C:H at areas of low fluxes is a possible additional hydrogen sink, which could be effective during the wall pumping phenomenon

Nanostructured carbon thin films have been actively investigated recently for their electroresistance (ER) properties. Furthermore, carbon films with nonlinear current-voltage (I-V) characteristics have potential application in field-emission devices. This has motivated us to study the effect of various growth parameters on the physical and morphological properties of carbon films grown by pulsed laser deposition (PLD). Carbon films have been deposited using a graphite target at different partial pressures of argon. The morphology of film surfaces deposited at various growth conditions was monitored using an atomic force microscope (AFM). AFM studies showed nanostructured grain growth with average grain size of about 80-90 nm. As the deposition time was decreased down to 1 min, the grain size was also found to decrease correspondingly. From Raman spectroscopic measurements an increase in the I(D)/I(G) ratio and a decrease in FWHM (G) clearly revealed the promotion of sp 2 hybridization as the substrate temperature increased. All the films show semiconducting behaviour with the dominant conduction process being the three-dimensional (3D) variable range hopping (VRH) mechanism. Nonlinear I-V curves were obtained for carbon films deposited on p-type Si indicating diode-like behaviour. The most significant result of this study was the observation of a large electroresistance value

A new mode for hydrogen adsorption and storage in single-wall carbon nano-tubes is used, on the basis of laser excitation. Remember that this method has been useful to obtain, in the case of the fullerene C 60 , many complex C 60 -atoms or C 60 -molecules, where atoms or molecular particles are trapped inside the C 60 -molecules. We think this method might be important to store many hydrogen molecules inside carbon nano-tubes. (author)

Undoped and Ca-O-modified diamond-like carbon coatings were deposited by a direct current discharge. Hardness and Young's modulus of Ca-O-modified DLCs were reduced in comparison with the undoped DLC, but the adherence of the Ca-O-modified films is improved. Ca-O-modified DLCs have a higher fraction of nano-crystalline regions with carbon in sp2 hybridisation. In addition, an increased oxygen content and CaCO3 was identified in Ca-O-modified DLCs. While mouse fibroblasts of the type L929 attach and grow on unmodified diamond-like carbon coatings synthesized by the decomposition of hydrocarbon, the addition of CaO-H2O into the precursor gas improves the coatings biological acceptance by the cells.

A molten metal reactor for converting a carbon material and steam into a gas comprising hydrogen, carbon monoxide, and carbon dioxide is disclosed. The reactor includes an interior crucible having a portion contained within an exterior crucible. The interior crucible includes an inlet and an outlet; the outlet leads to the exterior crucible and may comprise a diffuser. The exterior crucible may contain a molten alkaline metal compound. Contained between the exterior crucible and the interior crucible is at least one baffle.

This is a summary for work performed under cooperative agreement DE FC36 04GO14006 (Design and Development of New Carbon-based Sorbent Systems for an Effective Containment of Hydrogen). The project was directed to discover new solid and liquid materials that use reversible catalytic hydrogenation as the mechanism for hydrogen capture and storage. After a short period of investigation of solid materials, the inherent advantages of storing and transporting hydrogen using liquid-phase materials focused our attention exclusively on organic liquid hydrogen carriers (liquid carriers). While liquid carriers such as decalin and methylcyclohexane were known in the literature, these carriers suffer from practical disadvantages such as the need for very high temperatures to release hydrogen from the carriers and difficult separation of the carriers from the hydrogen. In this project, we were successful in using the prediction of reaction thermodynamics to discover liquid carriers that operate at temperatures up to 150 C lower than the previously known carriers. The means for modifying the thermodynamics of liquid carriers involved the use of certain molecular structures and incorporation of elements other than carbon into the carrier structure. The temperature decrease due to the more favorable reaction thermodynamics results in less energy input to release hydrogen from the carriers. For the first time, the catalytic reaction required to release hydrogen from the carriers could be conducted with the carrier remaining in the liquid phase. This has the beneficial effect of providing a simple means to separate the hydrogen from the carrier.

A series of Cobalt-Carbon, Cobalt-Molybdenum-Carbon catalysts were prepared by impregnation. The molar ratios of Co:Mo were 9:1, 8:2 and 7:3 and the total metal weights of them in the supported catalysts were 5 wt%. Moreover, the effects of reaction temperature and the Co:Mo molar ratios on the produce hydrogen and carbon nanotubes were investigated systematically. Of all the catalysts, Co-Mo (5 wt%, Co:Mo = 9:1)/C was the most effective one on the basis of hydrogen yield (84%), ethanol conversion (95%) and the quality of carbon nanotubes at 600 °C. A small amount of Mo added into the Co/C catalysts resulted in increasing in the yield of hydrogen and improving on quality of carbon nanotubes from ethanol decomposition over the Co-Mo catalysts.

Using ferrocene, H2 and O2, Carbon nanomaterials were prepared with gaseous detonation (deflagration) method. The effects of H2 on the phase and morphology of carbon nanomaterials were studied by various proportions of H2 in the reaction. The prepared samples were characterized by x-ray diffractometer, transmission electron microscope and Raman spectrometer. The results show that hydrogen proportion has a great influence on the phase and morphology of carbon nanomaterials. The high hydrogen proportion leads to much unreacted hydrogen, which could protect the iron atom from oxidation of carbon and dilute the reactants contributing to uniform particle size. In addition, the graphitization degree of multi-walled carbon nanotubes, observed in samples with high H2 proportion, is high enough to see the lattice fringes, but the degree of graphitization of whole sample is lower than which fabricated with low H2 proportion, and it may result from the low energy generation.

Structural phase transformation from multiwalled carbon nanotubes to nanocrystalline diamond by hydrogen plasma post-treatment was carried out. Ultrahigh equivalent diamond nucleation density above 10 11 nuclei/cm 2 was easily obtained. The diamond formation and growth mechanism was proposed to be the consequence of the formation of sp 3 bonded amorphouscarbon clusters. The hydrogen chemisorption on curved graphite network and the energy deposited on the carbon nanotubes by continuous impingement of activated molecular or atomic hydrogen are responsible for the formation of amorphouscarbon matrix. The diamond nucleates and grows in the way similar to that of diamond CVD processes on amorphouscarbon films. The present method of hydrogen treatment provides a controllable way for the CVD of high quality diamond films

After a brief presentation of the current use of hydrogen in industrial processes, of its potential as an energy vector, and of processes and of their costs, and an indication of the origin of hydrogen produced in the world in 2011, this publication describes how, according to a low carbon logics, hydrogen will be a substitution to fossil products. It describes how hydrogen can be used in transports (internal combustion engine, fuel cell), or for the formation of hythane (a mixing with methane in natural gas networks). It finally briefly outlines remaining technological, economic, safety-related and social locks which are still to be solved for these developments

In this study, we introduce highly active, efficient, and Pt-free electrodes (Cu@Ni-P@a-MoS2) fabricated on Ni foils, which have good conductivity and several a-MoS2 edge sites for the hydrogen evolution reaction (HER). A porous Cu dendritic structure on Ni foil was made by electro-plating utilizing hydrogen bubbles, and a Ni-P film that covered the dendritic structure was made by electro-less plating. Vertically grown a-MoS2 nanosheets were formed on the Cu@Ni-P dendritic structure by thermolysis. The structure has abundant active sites because of its particular structure, which was examined by SEM and TEM. XPS analysis was used to confirm that MoS2 was reduced completely, and the a-MoS2 nanosheet layer was characterized by Raman spectroscopy. Electrochemical experiments demonstrated that the electrode was highly effective for the HER with a low onset potential of 118.5 mV, and a current density of 10 and 100 mA/cm2 for 186 and 345 mV versus the reversible hydrogen electrode potential (vs RHE), respectively, a small Tafel slope of 60.5 mV/dec, and was stable after 2000 cycles. This study demonstrates that highly porous Cu@Ni-P@a-MoS2 electrodes, possessing a huge surface, are desirable for the HER and these findings will pave the way for a new form of highly efficient electrocatalysts.

assumptions in a variety of detectors. The library also includes simple particle transportation or can be interfaced to external transport codes. We applied our code to RL and OSL data from fiber-coupled Al2O3:C-detectors in a proton (nominal energies 10 MeV to 60 MeV) and a carbon beam (270 MeV/u). Results...

Concern has been expressed that hydrogen produced by corrosion, radiolysis, and decomposition of the waste could cause embrittlement of the carbon steel waste tanks at Hanford. The concern centers on the supposition that the hydrogen evolved in many of the existing tanks might penetrate the steel wall of the tank and cause embrittlement that might lead to catastrophic failure. This document reviews literature on the effects of hydrogen on the carbon steel proposed for use in the Multi-Function Waste Tank Facility for the time periods before and during construction as well as for the operational life of the tanks. The document draws several conclusions about these effects. Molecular hydrogen is not a concern because it is not capable of entering the steel tank wall. Nascent hydrogen produced by corrosion reactions will not embrittle the steel because the mild steel used in tank construction is not hard enough to be susceptible to hydrogen stress cracking and the corrosion product hydrogen is not produced at a rate sufficient to cause either loss in tensile ductility or blistering. If the steel intended for use in the tanks is produced to current technology, fabricated in accordance with good construction practice, postweld heat treated, and operated within the operating limits defined, hydrogen will not adversely affect the carbon steel tanks during their 50-year design life. 26 refs

Storage and transportation of hydrogen is a major obstacle for its use as a fuel. An increasingly considered alternative for the direct handling of hydrogen is to use carbon dioxide (CO2) as an intermediate storage material. However, CO2 is thermodynamically stable, and developed chemical catalysts often require high temperatures, pressures, and/or additives for high catalytic rates. Here, we present the discovery of a bacterial hydrogen-dependent carbon dioxide reductase from Acetobacterium woodii directly catalyzing the hydrogenation of CO2. We also demonstrate a whole-cell system able to produce formate as the sole end product from dihydrogen (H2) and CO2 as well as syngas. This discovery opens biotechnological alternatives for efficient CO2 hydrogenation either by using the isolated enzyme or by employing whole-cell catalysis.

Full Text Available Herein, we report on a novel method for deposition of magnesium (Mg nanoparticles at the surface of carbon materials. Through the suspension of carbon nanotubes (CNTs in an electrolyte containing di-n-butylmagnesium as a precursor, Mg nanoparticles were effectively deposited at the surface of the CNTs as soon as these touched the working electrode. Through this process, CNTs supported Mg particles as small as 1 nm were synthesized and the distribution of the nanoparticles was found to be influenced by the concentration of the CNTs in the electrolyte. Hydrogenation of these nanoparticles at 100°C was found to lead to low temperature hydrogen release starting at 150°C, owing to shorter diffusion paths and higher hydrogen mobility in small Mg particles. However, these hydrogen properties drastically degraded as soon as the hydrogenation temperature exceeded 200°C and this may be related to the low melting temperature of ultrasmall Mg particles.

Shen, Chaoqi; Aguey-Zinsou, Kondo-Francois, E-mail: f.aguey@unsw.edu.au [MERLin, School of Chemical Engineering, The University of New South Wales, Sydney, NSW (Australia)

2017-10-17

Herein, we report on a novel method for deposition of magnesium (Mg) nanoparticles at the surface of carbon materials. Through the suspension of carbon nanotubes (CNTs) in an electrolyte containing di-n-butylmagnesium as a precursor, Mg nanoparticles were effectively deposited at the surface of the CNTs as soon as these touched the working electrode. Through this process, CNTs supported Mg particles as small as 1 nm were synthesized and the distribution of the nanoparticles was found to be influenced by the concentration of the CNTs in the electrolyte. Hydrogenation of these nanoparticles at 100°C was found to lead to low temperature hydrogen release starting at 150°C, owing to shorter diffusion paths and higher hydrogen mobility in small Mg particles. However, these hydrogen properties drastically degraded as soon as the hydrogenation temperature exceeded 200°C and this may be related to the low melting temperature of ultrasmall Mg particles.

Full Text Available Amorphouscarbon films can be prepared with a large variety of structure and have been used in a number of technological applications. Many of their properties have been determined, but very little is known concerning the effect of pressure on their properties. In this work we investigate the influence of pressure of graphite-like amorphouscarbon films on the density of states (DOS using X-ray Excited Auger Electron Spectroscopy (XAES and the second derivate method of the XAES. The films were deposited by ion beam deposition and simultaneously bombarded with argon, which is responsible for the variation of the film stress, reaching extremely high values (4.5 GPa. Marked variations of the density of states of the pπ, pσ, sp, and s components were observed with increasing stress.

In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support

The discovery of oxygen and carbon monoxide tolerant [NiFe] hydrogenases was the first necessary step toward the definition of a novel generation of hydrogen fed biofuel cells. The next important milestone is now to identify and overcome bottlenecks limiting the current densities, hence the power densities. In the present work we report for the first time a comprehensive study of herringbone carbon nanofiber mesoporous films as platforms for enhanced biooxidation of hydrogen. The 3D network allows mediatorless hydrogen oxidation by the membrane-bound hydrogenase from the hyperthermophilic bacterium Aquifex aeolicus. We investigate the key physico-chemical parameters that enhance the catalytic efficiency, including surface chemistry and hierarchical porosity of the biohybrid film. We also emphasize that the catalytic current is limited by mass transport inside the mesoporous carbon nanofiber film. Provided hydrogen is supplied inside the carbon film, the combination of the hierarchical porosity of the carbon nanofiber film with the hydrophobicity of the treated carbon material results in very high efficiency of the bioelectrode. By optimization of the whole procedure, current densities as high as 4.5 mA cm(-2) are reached with a turnover frequency of 48 s(-1). This current density is almost 100 times higher than when hydrogenase is simply adsorbed at a bare graphite electrode, and more than 5 times higher than the average of the previous reported current densities at carbon nanotube modified electrodes, suggesting that carbon nanofibers can be efficiently used in future sustainable H2/O2 biofuel cells.

Nanoparticles on carbon nanotubes can be used as a high surface area catalyst or as a means to produce well-defined particles. In this study, cobalt nanoparticles were formed on xxsingle-walled carbon nanotubes during hydrogen exposure at an elevated temperature. The average particle size increased

A multielectrolytic modified carbon electrode (MEMCE) was fabricated by the electrolytic-oxidation/reduction processes. First, the functional groups containing nitrogen atoms such as amino group were introduced by the electrode oxidation of carbon felt electrode in an ammonium carbamate aqueous solution, and next, this electrode was electroreduced in sulfuric acid. The redox waves between hydrogen ion and hydrogen molecule at highly positive potential range appeared in the cyclic voltammogram obtained by MEMCE. A coulometric cell using MEMCE with a catalytic activity of electrooxidation of hydrogen molecule was constructed and was used for the measurement of dissolved hydrogen. The typical current vs. time curve was obtained by the repetitive measurement of the dissolved hydrogen. These curves indicated that the measurement of dissolved hydrogen was finished completely in a very short time (ca. 10 sec). A linear relationship was obtained between the electrical charge needed for the electrooxidation process of hydrogen molecule and dissolved hydrogen concentration. This indicates that the developed coulometric method can be used for the determination of the dissolved hydrogen concentration.